WO1998016587A1 - Azo compounds and process for preparing the same - Google Patents

Azo compounds and process for preparing the same Download PDF

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Publication number
WO1998016587A1
WO1998016587A1 PCT/JP1997/003637 JP9703637W WO9816587A1 WO 1998016587 A1 WO1998016587 A1 WO 1998016587A1 JP 9703637 W JP9703637 W JP 9703637W WO 9816587 A1 WO9816587 A1 WO 9816587A1
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Prior art keywords
group
carbon atoms
branch
substituent
azo compound
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PCT/JP1997/003637
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French (fr)
Japanese (ja)
Inventor
Ryuzo Ueno
Masaya Kitayama
Kenji Minami
Hiroyuki Wakamori
Original Assignee
Kabushiki Kaisha Ueno Seiyaku Oyo Kenkyujo
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Application filed by Kabushiki Kaisha Ueno Seiyaku Oyo Kenkyujo filed Critical Kabushiki Kaisha Ueno Seiyaku Oyo Kenkyujo
Priority to US09/068,954 priority Critical patent/US5973126A/en
Priority to CA 2239119 priority patent/CA2239119A1/en
Priority to JP51818398A priority patent/JP3224397B2/en
Priority to EP97943169A priority patent/EP0881267B1/en
Priority to JP51818198A priority patent/JP3393869B2/en
Priority to DE69728860T priority patent/DE69728860T2/en
Priority to AT97943169T priority patent/ATE265498T1/en
Priority to KR10-1998-0703755A priority patent/KR100472978B1/en
Publication of WO1998016587A1 publication Critical patent/WO1998016587A1/en

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    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D213/00—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members
    • C07D213/02—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members having three double bonds between ring members or between ring members and non-ring members
    • C07D213/04—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members having three double bonds between ring members or between ring members and non-ring members having no bond between the ring nitrogen atom and a non-ring member or having only hydrogen or carbon atoms directly attached to the ring nitrogen atom
    • C07D213/60—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members having three double bonds between ring members or between ring members and non-ring members having no bond between the ring nitrogen atom and a non-ring member or having only hydrogen or carbon atoms directly attached to the ring nitrogen atom with hetero atoms or with carbon atoms having three bonds to hetero atoms with at the most one bond to halogen, e.g. ester or nitrile radicals, directly attached to ring carbon atoms
    • C07D213/72—Nitrogen atoms
    • C07D213/75—Amino or imino radicals, acylated by carboxylic or carbonic acids, or by sulfur or nitrogen analogues thereof, e.g. carbamates
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D233/00—Heterocyclic compounds containing 1,3-diazole or hydrogenated 1,3-diazole rings, not condensed with other rings
    • C07D233/54—Heterocyclic compounds containing 1,3-diazole or hydrogenated 1,3-diazole rings, not condensed with other rings having two double bonds between ring members or between ring members and non-ring members
    • C07D233/66—Heterocyclic compounds containing 1,3-diazole or hydrogenated 1,3-diazole rings, not condensed with other rings having two double bonds between ring members or between ring members and non-ring members with hetero atoms or with carbon atoms having three bonds to hetero atoms with at the most one bond to halogen, e.g. ester or nitrile radicals, directly attached to ring carbon atoms
    • C07D233/88—Nitrogen atoms, e.g. allantoin
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D233/00—Heterocyclic compounds containing 1,3-diazole or hydrogenated 1,3-diazole rings, not condensed with other rings
    • C07D233/54—Heterocyclic compounds containing 1,3-diazole or hydrogenated 1,3-diazole rings, not condensed with other rings having two double bonds between ring members or between ring members and non-ring members
    • C07D233/66—Heterocyclic compounds containing 1,3-diazole or hydrogenated 1,3-diazole rings, not condensed with other rings having two double bonds between ring members or between ring members and non-ring members with hetero atoms or with carbon atoms having three bonds to hetero atoms with at the most one bond to halogen, e.g. ester or nitrile radicals, directly attached to ring carbon atoms
    • C07D233/90—Carbon atoms having three bonds to hetero atoms with at the most one bond to halogen, e.g. ester or nitrile radicals
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D235/00—Heterocyclic compounds containing 1,3-diazole or hydrogenated 1,3-diazole rings, condensed with other rings
    • C07D235/02—Heterocyclic compounds containing 1,3-diazole or hydrogenated 1,3-diazole rings, condensed with other rings condensed with carbocyclic rings or ring systems
    • C07D235/04—Benzimidazoles; Hydrogenated benzimidazoles
    • C07D235/24—Benzimidazoles; Hydrogenated benzimidazoles with hetero atoms or with carbon atoms having three bonds to hetero atoms with at the most one bond to halogen, e.g. ester or nitrile radicals, directly attached in position 2
    • C07D235/26—Oxygen atoms
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D277/00—Heterocyclic compounds containing 1,3-thiazole or hydrogenated 1,3-thiazole rings
    • C07D277/02—Heterocyclic compounds containing 1,3-thiazole or hydrogenated 1,3-thiazole rings not condensed with other rings
    • C07D277/20—Heterocyclic compounds containing 1,3-thiazole or hydrogenated 1,3-thiazole rings not condensed with other rings having two or three double bonds between ring members or between ring members and non-ring members
    • C07D277/32—Heterocyclic compounds containing 1,3-thiazole or hydrogenated 1,3-thiazole rings not condensed with other rings having two or three double bonds between ring members or between ring members and non-ring members with hetero atoms or with carbon atoms having three bonds to hetero atoms with at the most one bond to halogen, e.g. ester or nitrile radicals, directly attached to ring carbon atoms
    • C07D277/38—Nitrogen atoms
    • C07D277/44—Acylated amino or imino radicals
    • C07D277/46—Acylated amino or imino radicals by carboxylic acids, or sulfur or nitrogen analogues thereof
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D277/00—Heterocyclic compounds containing 1,3-thiazole or hydrogenated 1,3-thiazole rings
    • C07D277/60—Heterocyclic compounds containing 1,3-thiazole or hydrogenated 1,3-thiazole rings condensed with carbocyclic rings or ring systems
    • C07D277/62—Benzothiazoles
    • C07D277/68—Benzothiazoles with hetero atoms or with carbon atoms having three bonds to hetero atoms with at the most one bond to halogen, e.g. ester or nitrile radicals, directly attached in position 2
    • C07D277/82—Nitrogen atoms
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D401/00—Heterocyclic compounds containing two or more hetero rings, having nitrogen atoms as the only ring hetero atoms, at least one ring being a six-membered ring with only one nitrogen atom
    • C07D401/02—Heterocyclic compounds containing two or more hetero rings, having nitrogen atoms as the only ring hetero atoms, at least one ring being a six-membered ring with only one nitrogen atom containing two hetero rings
    • C07D401/12—Heterocyclic compounds containing two or more hetero rings, having nitrogen atoms as the only ring hetero atoms, at least one ring being a six-membered ring with only one nitrogen atom containing two hetero rings linked by a chain containing hetero atoms as chain links
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D403/00—Heterocyclic compounds containing two or more hetero rings, having nitrogen atoms as the only ring hetero atoms, not provided for by group C07D401/00
    • C07D403/02—Heterocyclic compounds containing two or more hetero rings, having nitrogen atoms as the only ring hetero atoms, not provided for by group C07D401/00 containing two hetero rings
    • C07D403/12—Heterocyclic compounds containing two or more hetero rings, having nitrogen atoms as the only ring hetero atoms, not provided for by group C07D401/00 containing two hetero rings linked by a chain containing hetero atoms as chain links
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D417/00—Heterocyclic compounds containing two or more hetero rings, at least one ring having nitrogen and sulfur atoms as the only ring hetero atoms, not provided for by group C07D415/00
    • C07D417/02—Heterocyclic compounds containing two or more hetero rings, at least one ring having nitrogen and sulfur atoms as the only ring hetero atoms, not provided for by group C07D415/00 containing two hetero rings
    • C07D417/12—Heterocyclic compounds containing two or more hetero rings, at least one ring having nitrogen and sulfur atoms as the only ring hetero atoms, not provided for by group C07D415/00 containing two hetero rings linked by a chain containing hetero atoms as chain links
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09B—ORGANIC DYES OR CLOSELY-RELATED COMPOUNDS FOR PRODUCING DYES, e.g. PIGMENTS; MORDANTS; LAKES
    • C09B29/00—Monoazo dyes prepared by diazotising and coupling
    • C09B29/10—Monoazo dyes prepared by diazotising and coupling from coupling components containing hydroxy as the only directing group
    • C09B29/103—Monoazo dyes prepared by diazotising and coupling from coupling components containing hydroxy as the only directing group of the naphthalene series
    • C09B29/106—Hydroxy carboxylic acids of the naphthalene series
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09B—ORGANIC DYES OR CLOSELY-RELATED COMPOUNDS FOR PRODUCING DYES, e.g. PIGMENTS; MORDANTS; LAKES
    • C09B29/00—Monoazo dyes prepared by diazotising and coupling
    • C09B29/10—Monoazo dyes prepared by diazotising and coupling from coupling components containing hydroxy as the only directing group
    • C09B29/18—Monoazo dyes prepared by diazotising and coupling from coupling components containing hydroxy as the only directing group ortho-Hydroxy carbonamides
    • C09B29/20—Monoazo dyes prepared by diazotising and coupling from coupling components containing hydroxy as the only directing group ortho-Hydroxy carbonamides of the naphthalene series
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
    • Y10S—TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10S534/00—Organic compounds -- part of the class 532-570 series
    • Y10S534/04—Azo compounds which are lakes

Definitions

  • the present invention relates to a novel azo compound and a method for producing the same.
  • the azo pigments are synthesized by a coupling reaction between a diazo compound and a coupler ( of which couplers of particular importance are 2-hydroxynaphthalene-13-carboxylic acid or its derivatives.
  • Prillant-Carmine 6B (Pigment Red 57), a pigment synthesized from 2-hydroxynaphthalene-13-carboxylic acid (Pigment Red 48), is the most important red-soluble azo pigment. These are used in the form of insoluble metal lakes such as Ca, Ba, and Mn, but are inherently unstable to acids and alkalis because they are metal salts.
  • an insoluble azo pigment is synthesized by using 2-hydroxynaphthalene-13-anilide, which is synthesized by condensation of 2-hydroxynaphthalene-13-carboxylic acid and an aniline, as a coupler.
  • This so-called naphthol pigment has been developed for the purpose of improving solubility and fastness, and is generally superior to azo lake pigment in properties such as light resistance, weather resistance, chemical resistance and solvent resistance.
  • azo pigments derived from 2-hydroxynaphthalene-16-carboxylic acid which is an isomer of 2-hydroxynaphthalene-3-carboxylic acid, and their properties are also known (Japanese Unexamined Patent Publication No. 2-302). 4 7 1).
  • the present invention is characterized by obtaining a novel azo-based coloring material excellent in water resistance, chemical resistance, solvent resistance and the like.
  • the present invention relates to 2-hydroxynaphthalene-1,3,6-dicarboxylic acids, esters, A novel azo compound using an amide or peridode derivative as a coupler, a coloring material containing the azo compound, and a method for producing the azo compound are provided. That is, the present invention provides the following general formula [1]:
  • X and X ′ may be the same or different, and may have an aromatic group which may have a substituent or a heterocyclic group having a conjugated double bond which may have a substituent) ,
  • R and R ' may be the same or different, and each may be a hydroxyl group, an alkoxy group having 1 to 6 carbon atoms which may have a branch, a benzyloxy group, a phenyloxy group or a phenacyloxy group (where R or R ', If either is a hydroxyl group, may form an acceptable salt),
  • n an integer of 1 or 2
  • R 2 is a hydrogen atom, an alkyl group having 1 to 6 carbon atoms which may have a branch, an acyl group or a phenylalkyl group having 1 to 6 carbon atoms,
  • Q represents an alkyl group having 1 to 6 carbon atoms which may have a branch; an alkoxy group having 1 to 6 carbon atoms which may have a branch, a halogen atom, a nitro group or a nitroso group.
  • M is an integer of 0 to 3 (when m is 1, Q may be bonded to either of two fused rings, and when m is 2 or 3, Q is bonded to one or both fused rings. And a ring with two fused rings May be formed) and
  • Z represents a monovalent aromatic group which may have a substituent.
  • the azo compound represented by the formula [1], a method for producing the azo compound, and a coloring material containing the azo compound are referred to herein as a coloring material such as a dye, a pigment, an ink, a paint, a printing ink, and a charge generating material.
  • the present invention further relates to a compound of the general formula [II]
  • X and X ′ may be the same or different, and may have an aromatic group which may have a substituent or a heterocyclic group having a conjugated double bond which may have a substituent) ,
  • R and R ′ may be the same or different, a hydroxyl group, an alkoxy group having 1 to 6 carbon atoms which may have a branch, a benzyloxy group, a phenyloxy group or a phenacyloxy group,
  • n is an integer of 1 or 2
  • R 2 is a hydrogen atom, an alkyl group having 1 to 6 carbon atoms which may have a branch, an acyl group or a phenylalkyl group having 1 to 6 carbon atoms
  • Q represents an alkyl group having 1 to 6 carbon atoms which may have a branch, an alkoxy group having 1 to 6 carbon atoms which may have a branch, a halogen atom, a nitro group or a nitroso group
  • m is an integer of 0 to 3 (when m is 1, Q may be bonded to either of the two fused rings, and when m is 2 or 3, Q is bonded to one or both fused rings. And may form a ring together with the two condensed rings).
  • Y is one (C O NH) n—X or one C O R,
  • X and X ′ may be the same or different, and may have an aromatic group which may have a substituent or a heterocyclic group having a conjugated double bond which may have a substituent) ,
  • R and R ′ may be the same or different, a hydroxyl group, an alkoxy group having 1 to 6 carbon atoms which may have a branch, a benzyloxy group, a phenyloxy group, a phenyl group, a phenacyloxy group,
  • n an integer of 1 or 2
  • R 2 is a hydrogen atom, an alkyl group having 1 to 6 carbon atoms which may have a branch, an acyl group or a phenylalkyl group having 1 to 6 carbon atoms,
  • Q is an alkyl group having 1 to 6 carbon atoms which may have a branch, An alkoxy group, a halogen atom, a nitro group or a nitroso group having 1 to 6 carbon atoms which may have a branch, m is an integer of 0 to 3 (when m is 1, Q represents two fused rings And when m is 2 or 3, Q may be bonded to one or both condensed rings, or may form a ring together with the two condensed rings.)
  • Z represents a monovalent aromatic group which may have a substituent.
  • the force Wupler uses 2-hydroxynaphthalene-13,6-dicarboxyamide, perylene or a carboxylic acid derivative as a raw material.
  • the starting material, 2-hydroxynaphthalene-1,3,6-dicarboxylic acid is a Kolbe-Schmitt method in which carbon dioxide is reacted with 2-hydroxynaphthalene potassium under high temperature and high pressure in the presence of potassium salt such as naphthol potassium.
  • potassium salt such as naphthol potassium
  • the amide or peridode can be obtained by obtaining an acid chloride in a solvent such as sulfolane using thionyl chloride or the like according to a conventional method, and reacting the acid chloride with an amine or urea. Alternatively, it can be obtained by directly reacting with amines and ureas with phosphorus trichloride or dicyclohexylcarbodiimide.
  • Examples of the amines or ureas that is, the compounds constituting the group X or X ′ in Y and Y ′ include aromatic amino compounds which may have a substituent, for example, aniline (where X or X ′ is a fuunyl group) ), One or one aminonaphthalene (X or X 'is a naphthyl group), aminoanthraquinone (X or X' is an anthraquinonyl group), a heterocyclic compound having a conjugated double bond which may have a substituent, For example, an aminobenzimidazolone (X or X 'is a benzimidazolonyl group), an aminocarbazole (X or X' is a carbazolyl group), Aminoviridine (X or X 'is a pyridyl group), Aminothiazole (X or X' is a thiazolyl group), Aminobenzothiazole (X or
  • substituent of these compounds include halogen, nitro group, lower alkyl group, lower alkoxy group, cyano group, phenoxy group, amide group (for example, phenylaminocarbonyl group), and the like.
  • substituents include other substituents such as halogen, lower alkyl, lower alkoxy, alkylaminosulfonyl, nitrile and the like.
  • phenylurea can be obtained from aniline.
  • Y and Y ′ may represent one COR or one COR ′.
  • R and R ′ may be the same or different, and may be a hydroxyl group, an alkoxy group having 1 to 6 carbon atoms, and preferably having 1 to 4 carbon atoms, particularly a methoxy group or an ethoxy group; It represents a benzyloxy group, a phenoxy group or a phenacyloxy group, and the aromatic ring contained in these groups may have a substituent, for example, a halogen atom or a lower alkyl group. .,
  • the group R 2 is a hydrogen atom, an alkyl group having 1 to 6, preferably 1 to 4 carbon atoms, which may have a branch, especially a methyl group or an ethyl group; Or an acetyl group; or a phenylalkyl group, and a fuunylalkyl group is a substituent such as a halogen atom, a lower alkyl group. It may have a kill group or the like.
  • the group Q means that it may have a substituent on the naphthalene nucleus
  • Q is an alkyl group having 1 to 6, preferably 1 to 4 carbon atoms, which may have a branch, especially a methyl group, An ethyl group; an alkoxy group having 1 to 6, preferably 1 to 4 carbon atoms which may have a branch, especially a methoxy group, an ethoxy group; a halogen atom, a nitro group or a nitroso group.
  • the number m of the substituents is usually 0, but may have up to 3. However, it does not have a substituent at the 1-position of the naphthalene nucleus. Further, when m is 1, Q may be bonded to either of the two fused rings, when m is 2 or 3, Q may be bonded to one or both fused rings, and May form a ring together with the condensed ring of the above.
  • the azo compound of the present invention is a diazo compound obtained by diazotizing an aromatic amine represented by the general formula [II] with sodium nitrite or the like to obtain the 2-hydroxynaphthalene-1,3,6-dicarboxylic acid and It can be obtained by coupling with a derivative (for example, carboxyamide or carboxyperide or ester).
  • R or R ' is a hydroxyl group
  • it can be obtained by lake formation with an appropriate metal salt, for example, a salt of Ca, Ba, Mn, St or the like.
  • Aromatic amines that is, compounds constituting Z in the azo group include Rinylin (Z is a phenyl group), Hiichi or ⁇ -naphthylamine (Z is a naphthyl group), monoaminoanthracene.
  • monoaminoindene Z is an indenyl group
  • monoamino condensed polycyclic hydrocarbons such as monoaminofluorenone (Z is a fluorenyl group), monoaminoindole (Z is an indolyl group), monoaminobenzodithiophene (Z is benzothionyl group), monoaminoquinoline (Z is quinolinyl group), monoaminocarbazole (Z Is a carbazolyl group).
  • aromatic amines may have a substituent.
  • substituents examples include halogen, lower alkyl, especially methyl, cyano, nitro, lower alkoxy, amide, sulfonyl, and alkylaminosulfonyl groups. , ⁇ amino carbonyl group, Fuwenokishi group, an alkoxycarbonyl group, arsenate Dorokishi group, c particularly preferred aromatic Amin compounds etc. Benzoiruamino groups are exemplified good Anirin acids have a substituent (Z is phenyl group) or ⁇ - or / 3-naphthylamines ( ⁇ is a naphthyl group) which may have a substituent.
  • the method for obtaining the diazo compound from the amines is not particularly limited.
  • a general method for diazotizing aromatic primary amines with sodium nitrite may be used.
  • the diazo compound is further coupled with the above-mentioned 2-hydroxynaphthalene-13,6-dicaroxyamide, carboxyperide or ester, and a conventional method may be employed.
  • the azo compound of the present invention can be used for pigments, printing inks, paints, kneading coloring materials for polymer materials, and the like.
  • Example 2 The azo compound obtained in Example 1, a commercially available 2-hydroxy-3-phenylaminocarbonyl derivative (Comparative Example 1), and 2-hydroxy-6-phenyl described in JP-A-2-302471 Table 1 shows properties of the aminocarbonyl derivative (Comparative Example 2), such as water resistance, chemical resistance, solvent resistance, migration resistance, and light resistance as a baking paint.
  • Solvent resistance Add 1 part of sample to 20 parts of acetone, methanol or xylene and disperse by ultrasonic wave for 5 minutes. After filtration, the color of the filtrate was observed and evaluated according to A to E shown below.
  • Example 2 As the amine component, 2-methyl-5-nitroaniline of Example 1 was used. The same procedure as in Example 1 was repeated except that methoxy-5-phenylaminocarbonylaniline was used instead of 7.3 g and suspended in 50 g of water and 50 g of methanol. 6.8 g of red powder [2-hydroxy_1- (2, -methoxy-5'-phenylaminocarbonylphenylazo) -1,6-bisphenylaminocarbonylcarbonylnaphthalene] Obtained (melting point / decomposition point: 282.5 ° C (decomposition)).
  • Example 1 The 2-amine-5-nitroaniline of Example 1 was used as the amine component instead of the amine shown in Table 2 and suspended in 50 g of water and 50 g of methanol, and 2-hydroxy was used as the coupler component.
  • An azo compound was synthesized in the same manner as in Example 1 except that 1,3,6-bisphenylaminocarbonylnaphthalene was replaced with a force puller shown in Table 2.
  • Table 2 shows the melting points and decomposition points of the synthesized azo compounds.
  • amine component 1.46 g of 2-methoxy-5-phenylaminocarbonylaniline is suspended in 20 g of water, and 1.8 g of 35% hydrochloric acid is added. Then, while maintaining the temperature at 0 ° C, a solution of 0.84 g of sodium nitrite dissolved in 5 g of water is added dropwise to perform diazotization. Thereafter, 4 g of borofluoric acid is added, and the precipitated diazodium salt is filtered.
  • a flesh-colored crystal [2-hydroxy-3,6-bis] was prepared in the same manner as in Example 26 except that 8.3 g of 2-aminoaminothiazole in Example 26 was replaced with 8.3 g of 2-amino-4-dicyanomidazole. (4 ', 5'-dicyanimidazole —2′-ylaminocarbonyl) naphthalene] (3.5 g, melting point: 256.8.C).
  • Example 27 (2) The 2-hydroxy-1,3,6-bis (benzothiazole-2′-ylaminocarbonyl) naphthalene of Example 27 (2) was replaced with 2-hydroxy-1,3,6-bis (4 ′, 5'-dicyanimidazole-1'-ylaminocarbonyl) naphthalene 1.
  • a dark red powder [2-hydroxy) was prepared in the same manner as in Example 27 (2) except that 1.49 g was used.
  • Example 23 As the amine component, 4-aminotoluene-13-sulfonic acid of Example 23 was replaced with the amine shown in Table 3, and as the force-puppler component, 2-hydroxy-3,6-dihydroxycarbonyl naphthalene was used. Replace with power blebbers shown in Table 3 and use 1.1 times the amount of calcium chloride dihydrate An azo compound was synthesized in the same manner as in Example 23 except that the amount was changed to 1.2 times equivalent. In Examples 40, 41, and 42, barium chloride, strontium chloride, and manganese chloride were used in place of calcium chloride in Example 23, respectively. Table 3 shows the melting points and decomposition points of the synthesized azo compounds.
  • Example 39 With respect to the azo compounds obtained in Example 39, Example 54, and Example 64, a printing ink was prepared according to JIS K5101 and developed. Table 4 shows the color data. As the color data, the dominant wavelength d, the intensity of pure water P e, and the lightness Y shown in JIS Z8701 are shown. Table 4 Main Wavelength Hisago Stimulation Purity Pe Lightness Example 39 61 0 nra 58.1% 1.5% Example 54 6 19 nm 47.6% 8.5% Example 64 645 nm 32.2% 6.8%
  • a red powder [2-hydroxy-11- (2, -methoxy-1-5'-phenylaminocarbonylcarbonylphenyl) azo] was prepared in the same manner as in Example 27 (2) except that the amount was changed to 15 g. 3,6-bis (phenoxycarbonyl) naphthalene] 1.23 g was obtained. (Melting point / decomposition point: 328.8 ° C (decomposition)).
  • Example 77 was repeated in the same manner as in Example 77 except that 2-methoxy-5-phenylaminocarbonylylaniline of Example 77 was replaced by 0.42 g of 4-nitroaniline as a fluoramine component. Bluish red powder [2-Methoxy-11- (4'-nitrophenylazo) -13- (benzimidazolone-1 5 "-yl) -16-phenylaminocarbonylnaphthalene] 1.12 g was obtained (melting point / decomposition point: 323.3 ° C (decomposition)).
  • the azo compound of the present invention has a 2-carboxyl group (which may form a salt), a carboxyamide, a carboxyureide or an ester at positions 3 and 6 of 2-hydroxynaphthalene which is a coupler.
  • the coloring material obtained from this method is different from that obtained by using a forceps having these groups at other positions of 2-hydroxynaphthalene, or one carboxyamide, carboxyureide or Shows higher solvent resistance, water resistance and chemical resistance than those with esters.
  • FIG. 1 shows the infrared absorption spectrum of the azo compound of Example 1; and FIG. 2 shows the infrared absorption spectrum of the azo compound calcium salt of Example 23.

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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
  • Pyridine Compounds (AREA)
  • Inks, Pencil-Leads, Or Crayons (AREA)
  • Plural Heterocyclic Compounds (AREA)
  • Heat Sensitive Colour Forming Recording (AREA)
  • Cephalosporin Compounds (AREA)
  • Paints Or Removers (AREA)
  • Processes Of Treating Macromolecular Substances (AREA)
  • Thiazole And Isothizaole Compounds (AREA)
  • Heterocyclic Carbon Compounds Containing A Hetero Ring Having Nitrogen And Oxygen As The Only Ring Hetero Atoms (AREA)

Abstract

Novel monoazo compounds excellent in water, chemical and solvent resistances and other properties and synthesized by using 2-hydroxynaphthalene-3,6-dicarboxylic acid (or a salt thereof), amide, ureide, or an ester thereof as a coupler.

Description

明細書  Specification
ァゾ化合物およびその製法  Azo compounds and their preparation
技術分野 Technical field
本発明は新規ァゾ化合物およびその製法に関する。  The present invention relates to a novel azo compound and a method for producing the same.
背景技術 Background art
ァゾ顔料はジァゾ化合物とカプラーとのカップリング反応で合成される ( それらに使われるカプラーの中で特に重要なのは 2—ヒ ドロキシナフタレ ン一 3—力ルボン酸あるいはその誘導体である。 The azo pigments are synthesized by a coupling reaction between a diazo compound and a coupler ( of which couplers of particular importance are 2-hydroxynaphthalene-13-carboxylic acid or its derivatives.
2—ヒドロキシナフタレン一 3—カルボン酸から合成されるプリ リアン ト ·カーミン 6 B ( P igment Red 5 7 )ゃゥォチャングレツ ド（P igment Red 4 8 )は最も重要な赤色溶性ァゾ顔料である。 これらは C a、 B a、 M nなどの不溶性金属レーキの形で使用されているが金属塩であるから本 質的に酸、 アルカリに対し不安定である。  Prillant-Carmine 6B (Pigment Red 57), a pigment synthesized from 2-hydroxynaphthalene-13-carboxylic acid (Pigment Red 48), is the most important red-soluble azo pigment. These are used in the form of insoluble metal lakes such as Ca, Ba, and Mn, but are inherently unstable to acids and alkalis because they are metal salts.
一方、 2—ヒ ドロキシナフタレン一 3—カルボン酸とァニリン類との縮 合で合成される 2—ヒドロキシナフタレン一 3—ァニリ ドをカプラーと.し て不溶性ァゾ顔料が合成される。 このいわゆるナフトール顔料は溶解性や 堅牢性を改善する目的で開発されており、 一般的には耐光性、 耐候性、 耐 薬品性、 耐溶剤性などの性質においてァゾレーキ顔料に優る。  On the other hand, an insoluble azo pigment is synthesized by using 2-hydroxynaphthalene-13-anilide, which is synthesized by condensation of 2-hydroxynaphthalene-13-carboxylic acid and an aniline, as a coupler. This so-called naphthol pigment has been developed for the purpose of improving solubility and fastness, and is generally superior to azo lake pigment in properties such as light resistance, weather resistance, chemical resistance and solvent resistance.
また、 2—ヒドロキシナフタレン一 3—カルボン酸の異性体である 2— ヒドロキシナフタレン一 6—カルボン酸から誘導されるァゾ顔料およびそ の特性についても知られている（特開平 2— 3 0 2 4 7 1号）。  Further, azo pigments derived from 2-hydroxynaphthalene-16-carboxylic acid, which is an isomer of 2-hydroxynaphthalene-3-carboxylic acid, and their properties are also known (Japanese Unexamined Patent Publication No. 2-302). 4 7 1).
発明の開示 Disclosure of the invention
本発明は耐水性、 耐薬品性、 耐溶剤性などに優れた新規なァゾ系の色材 を得ることを特徴とする。  The present invention is characterized by obtaining a novel azo-based coloring material excellent in water resistance, chemical resistance, solvent resistance and the like.
本発明は 2—ヒドロキシナフタレン一 3， 6—ジカルボン酸、 エステル、 アミ ドまたはゥレイ ド誘導体をカップラーとして用いた新規なァゾ化合物、 それを含む色材および上記ァゾ化合物の製造法を提供する。 即ち、 本発明 は下記一般式 [ 1 ]： The present invention relates to 2-hydroxynaphthalene-1,3,6-dicarboxylic acids, esters, A novel azo compound using an amide or peridode derivative as a coupler, a coloring material containing the azo compound, and a method for producing the azo compound are provided. That is, the present invention provides the following general formula [1]:
Figure imgf000004_0001
Figure imgf000004_0001
〔式中、 Yは一 ( C〇N H)n— Xまたは一 C O R、 [Wherein Y is one (C〇NH) n—X or one COR,
Y'は一（C O N H)n— X'または一 C O R'、  Y 'is one (CONH) n—X' or one COR ',
(Xおよび X'は同じであっても異なっていてもよく、 置換基を有し ていてもよい芳香族基または置換基を有していてもよい共役二重結合を有 する複素環基)、  (X and X ′ may be the same or different, and may have an aromatic group which may have a substituent or a heterocyclic group having a conjugated double bond which may have a substituent) ,
Rおよび R'は同じであっても異なってもよい水酸基、 炭素原子 数が 1〜6の分岐を有してもよいアルコキシ基、 ベンジルォキシ基、 フヱ ニルォキシ基またはフヱナシルォキシ基（ただし、 Rまたは R'のいずれか —方が水酸基の場合は、 許容される塩を形成してもよい）、  R and R 'may be the same or different, and each may be a hydroxyl group, an alkoxy group having 1 to 6 carbon atoms which may have a branch, a benzyloxy group, a phenyloxy group or a phenacyloxy group (where R or R ', If either is a hydroxyl group, may form an acceptable salt),
nは 1または 2の整数を示す、  n represents an integer of 1 or 2,
R 2は水素原子、 炭素原子数が 1〜 6の分岐を有してもよいアル キル基、 炭素原子数が 1〜 6のァシル基またはフヱニルアルキル基、 R 2 is a hydrogen atom, an alkyl group having 1 to 6 carbon atoms which may have a branch, an acyl group or a phenylalkyl group having 1 to 6 carbon atoms,
Qは炭素原子数が 1〜 6の分岐を有していてもよいアルキル基、 ； 炭素原子数が 1〜6の分岐を有していてもよいアルコキシ基、 ハロゲン原 子、 ニトロ基またはニトロソ基、 mは 0 ~ 3の整数 （mが 1のとき Qは 2 個の縮合環のどちらに結合していてもよく、 mが 2または 3のとき Qは一 方または両方の縮合環に結合していてもよく、 また 2個の縮合環と共に環 を形成していてもよい） および Q represents an alkyl group having 1 to 6 carbon atoms which may have a branch; an alkoxy group having 1 to 6 carbon atoms which may have a branch, a halogen atom, a nitro group or a nitroso group. , M is an integer of 0 to 3 (when m is 1, Q may be bonded to either of two fused rings, and when m is 2 or 3, Q is bonded to one or both fused rings. And a ring with two fused rings May be formed) and
Zは置換基を有していてもよい 1価の芳香族基を表す。 〕で表さ れるァゾ化合物、 その製造方法およびこのァゾ化合物を含む色材に関する 本明細書で色材とは、 染料、 顔料、 インキ、 塗料、 印刷インキ、 電荷発生 材料などを言う。  Z represents a monovalent aromatic group which may have a substituent. The azo compound represented by the formula [1], a method for producing the azo compound, and a coloring material containing the azo compound are referred to herein as a coloring material such as a dye, a pigment, an ink, a paint, a printing ink, and a charge generating material.
本発明はさらに一般式 [II]  The present invention further relates to a compound of the general formula [II]
Z - N H 2 [II] Z-NH 2 [II]
〔式中、 Zは置換基を有していてもよい 1価の芳香族基を表す〕で表され る芳香族アミン類をジァゾ化し、 得られたジァゾ化合物を一般式 [ΠΙ]  [Wherein, Z represents a monovalent aromatic group which may have a substituent], and the obtained diazo compound is represented by the general formula [一般]
Figure imgf000005_0001
Figure imgf000005_0001
〔式中、 Yは一（C〇N H)n—Xまたは一 C O R、 [Where Y is one (C〇N H) n—X or one COR,
Y'は一（C O N H)n— X'または一 C O R 'ヽ  Y 'is one (C O N H) n—X' or one C O R 'ヽ
(Xおよび X'は同じであっても異なっていてもよく、 置換基を有し ていてもよい芳香族基または置換基を有していてもよい共役二重結合を有 する複素環基） 、  (X and X ′ may be the same or different, and may have an aromatic group which may have a substituent or a heterocyclic group having a conjugated double bond which may have a substituent) ,
Rおよび R'は同じであっても異なってもよい水酸基、 炭素原子 数が 1〜6の分岐を有してもよいアルコキシ基、 ベンジルォキシ基、 フエ ニルォキシ基またはフヱナシルォキシ基、  R and R ′ may be the same or different, a hydroxyl group, an alkoxy group having 1 to 6 carbon atoms which may have a branch, a benzyloxy group, a phenyloxy group or a phenacyloxy group,
nは 1または 2の整数、 および  n is an integer of 1 or 2, and
R 2は水素原子、 炭素原子数が 1〜 6の分岐を有してもよいアル キル基、 炭素原子数が 1〜 6のァシル基またはフヱニルアルキル基、 Qは炭素原子数が 1〜 6の分岐を有していてもよいアルキル基、 炭素原子数が 1〜6の分岐を有していてもよいアルコキシ基、 ハロゲン原 子、 ニトロ基またはニトロソ基、 mは 0〜3の整数 （mが 1のとき Qは 2 個の縮合環のどちらに結合していてもよく、 mが 2または 3のとき Qは一 方または両方の縮合環に結合していてもよく、 また 2個の縮合環と共に環 を形成していてもよい） を示す。 〕 R 2 is a hydrogen atom, an alkyl group having 1 to 6 carbon atoms which may have a branch, an acyl group or a phenylalkyl group having 1 to 6 carbon atoms, Q represents an alkyl group having 1 to 6 carbon atoms which may have a branch, an alkoxy group having 1 to 6 carbon atoms which may have a branch, a halogen atom, a nitro group or a nitroso group, m is an integer of 0 to 3 (when m is 1, Q may be bonded to either of the two fused rings, and when m is 2 or 3, Q is bonded to one or both fused rings. And may form a ring together with the two condensed rings). ]
で表される化合物とカップリングすることを特徴とする、 下記一般式 [ I ] Characterized by the following general formula [I]:
Figure imgf000006_0001
Figure imgf000006_0001
〔式中、 Yは一（C O NH)n—Xまたは一 C O R、 [Wherein, Y is one (C O NH) n—X or one C O R,
Y'は一（C O N H)n- X'または一 C O R'、  Y 'is one (CONH) n-X' or one COR ',
(Xおよび X'は同じであっても異なっていてもよく、 置換基を有し ていてもよい芳香族基または置換基を有していてもよい共役二重結合を有 する複素環基） 、  (X and X ′ may be the same or different, and may have an aromatic group which may have a substituent or a heterocyclic group having a conjugated double bond which may have a substituent) ,
Rおよび R'は同じであっても異なってもよい水酸基、 炭素原子 数が 1〜6の分岐を有してもよいアルコキシ基、 ベンジルォキシ基、 フエ ニルォキ,シ基またはフエナシルォキシ基、  R and R ′ may be the same or different, a hydroxyl group, an alkoxy group having 1 to 6 carbon atoms which may have a branch, a benzyloxy group, a phenyloxy group, a phenyl group, a phenacyloxy group,
nは 1または 2の整数を示す、  n represents an integer of 1 or 2,
R 2は水素原子、 炭素原子数が 1〜 6の分岐を有してもよいアル キル基、 炭素原子数が 1〜 6のァシル基またはフヱニルアルキル基、 R 2 is a hydrogen atom, an alkyl group having 1 to 6 carbon atoms which may have a branch, an acyl group or a phenylalkyl group having 1 to 6 carbon atoms,
Qは炭素原子数が 1〜 6の分岐を有していてもよいアルキル基、 炭素原子数が 1〜6の分岐を有していてもよいアルコキシ基、 ハロゲン原 子、 ニトロ基またはニトロソ基、 mは 0〜3の整数 （mが 1のとき Qは 2 個の縮合環のどちらに結合していてもよく、 mが 2または 3のとき Qは一 方または両方の縮合環に結合していてもよく、 また 2個の縮合環と共に環 を形成していてもよい） および Q is an alkyl group having 1 to 6 carbon atoms which may have a branch, An alkoxy group, a halogen atom, a nitro group or a nitroso group having 1 to 6 carbon atoms which may have a branch, m is an integer of 0 to 3 (when m is 1, Q represents two fused rings And when m is 2 or 3, Q may be bonded to one or both condensed rings, or may form a ring together with the two condensed rings.)
Zは置換基を有していてもよい 1価の芳香族基を表す。 〕で表さ れるァゾ化合物の製造法に関する。  Z represents a monovalent aromatic group which may have a substituent. And a process for producing an azo compound represented by the formula:
前述のごとく本発明においては力ップラー（一般式 [ΠΙ]で表される化合 物）は 2—ヒドロキシナフタレン一 3 , 6—ジカルボキシアミ ド、 ゥレイ ド またはカルボン酸誘導体を原料とする。 原料となる 2—ヒ ドロキシナフタ レン一 3， 6—ジカルボン酸はナフ トール力リウムなどの力リゥム塩の存 在下、 高温高圧下で二酸化炭素を 2—ヒドロキシナフタレンカリウムと反 応させるコルべシュミッ ト法により得ることができる。  As described above, in the present invention, the force Wupler (the compound represented by the general formula [ΠΙ]) uses 2-hydroxynaphthalene-13,6-dicarboxyamide, perylene or a carboxylic acid derivative as a raw material. The starting material, 2-hydroxynaphthalene-1,3,6-dicarboxylic acid, is a Kolbe-Schmitt method in which carbon dioxide is reacted with 2-hydroxynaphthalene potassium under high temperature and high pressure in the presence of potassium salt such as naphthol potassium. Can be obtained by
アミ ドまたはゥレイ ドは、 スルホランなどの溶媒中でチォニルクロリ ド などにより常法に従って酸クロリ ドを得、 これにアミン類ゃ尿素類を反応 することにより得ることができる。 あるいは三塩化りんまたはジシクロへ キシルカルボジィミ ドなどによりアミン類ゃ尿素類と直接反応することに よって得ることができる。  The amide or peridode can be obtained by obtaining an acid chloride in a solvent such as sulfolane using thionyl chloride or the like according to a conventional method, and reacting the acid chloride with an amine or urea. Alternatively, it can be obtained by directly reacting with amines and ureas with phosphorus trichloride or dicyclohexylcarbodiimide.
アミン類または尿素類、 即ち、 Yおよび Y'において基 Xまたは X'を構 成する化合物としては、 置換基を有していてもよい芳香族ァミノ化合物、 例えばァニリン（Xまたは X'がフユニル基）、 一または 一アミノナフ タレン（Xまたは X'がナフチル基）、 アミノアントラキノン（Xまたは X' がアントラキノニル基）、 置換基を有していてもよい共役二重結合を有す る複素環化合物、 例えばァミノベンズィミダゾロン（Xまたは X'がべンズ ィミダゾロニル基）、 ァミノカルバゾール（Xまたは X'が力ルバゾリル基）、 アミノビリジン（Xまたは X'がピリジル基）、 ァミノチアゾール（Xまたは X'がチアゾリル基）、 アミノベンゾチアゾール（Xまたは X'がべンゾチア ゾリル基）、 ァミノイミダゾ一ル （Xまたは X'がィミダゾリル基） 、 更に ァミノインドール （Xまたは X'がインドリル基） 、 アミノチォフェン （X または X'がチォニル基） 、 アミノフエノチアジン （Xまたは X'がフエノ チアジニル基） 、 アミノアクリジン （Xまたは X'がァクリジニル基） 、 ァミノキノリン （Xまたは X'がキノリニル基） などが例示される。 これ らの化合物の置換基としてはハロゲン、 ニトロ基、 低級アルキル基、 低級 アルコキシ基、 シァノ基、 フヱノキシ基、 アミ ド基（例えばフヱニルアミ ノカルボニル基）などが例示され、 更にこれらのフエノキシ基やアミ ド基 には別の置換基、 例えばハロゲン、 低級アルキル、 低級アルコキシ、 アル キルァミノスルホニル、 二トリルなどが例示される。 Examples of the amines or ureas, that is, the compounds constituting the group X or X ′ in Y and Y ′ include aromatic amino compounds which may have a substituent, for example, aniline (where X or X ′ is a fuunyl group) ), One or one aminonaphthalene (X or X 'is a naphthyl group), aminoanthraquinone (X or X' is an anthraquinonyl group), a heterocyclic compound having a conjugated double bond which may have a substituent, For example, an aminobenzimidazolone (X or X 'is a benzimidazolonyl group), an aminocarbazole (X or X' is a carbazolyl group), Aminoviridine (X or X 'is a pyridyl group), Aminothiazole (X or X' is a thiazolyl group), Aminobenzothiazole (X or X 'is a benzothiazolyl group), Aminoimidazole (X or X' is imidazolyl) ), Aminoaminodol (X or X 'is an indolyl group), aminothiophene (X or X' is a thionyl group), aminophenothiazine (X or X 'is a phenothiazinyl group), aminoacridine (X Or X 'is an acridinyl group), and amino quinoline (X or X' is a quinolinyl group). Examples of the substituent of these compounds include halogen, nitro group, lower alkyl group, lower alkoxy group, cyano group, phenoxy group, amide group (for example, phenylaminocarbonyl group), and the like. Examples of the substituent include other substituents such as halogen, lower alkyl, lower alkoxy, alkylaminosulfonyl, nitrile and the like.
上記ァミノ化合物とシアン酸力リを反応させる事により、 対応する尿素 を得ることができる。 即ち、 例えばァニリンからはフエニル尿素を得るこ とができる。  By reacting the above amino compound with cyanic acid, the corresponding urea can be obtained. That is, for example, phenylurea can be obtained from aniline.
Yおよび Y'は、 一 C O Rまたは一 C O R'を示してもよい。 Rおよび R 'は同じであっても異なっていてもよい水酸基、 炭素原子数 1〜6、 好ま しくは 1〜4の分岐を有していてもよいアルコキシ基、 特にメ トキシ基、 ェトキシ基；ベンジルォキシ基、 フヱノキシ基またはフエナシルォキシ基 を表すが、 これらの基に含まれる芳香族環は置換基、 例えばハロゲン原子、 低級アルキル基などを有していてもよい。 .，  Y and Y ′ may represent one COR or one COR ′. R and R ′ may be the same or different, and may be a hydroxyl group, an alkoxy group having 1 to 6 carbon atoms, and preferably having 1 to 4 carbon atoms, particularly a methoxy group or an ethoxy group; It represents a benzyloxy group, a phenoxy group or a phenacyloxy group, and the aromatic ring contained in these groups may have a substituent, for example, a halogen atom or a lower alkyl group. .,
基 R 2は水素原子、 炭素原子数 1〜6、 好ましくは 1〜4の分岐を有し ていてもよいアルキル基、 特にメチル基、 ェチル基；炭素原子数 1〜6、 好ましくは 1〜4のァシル基、 特にァセチル基； またはフヱニルアルキル 基であり、 フユニルアルキル基は置換基、 例えばハロゲン原子、 低級アル キル基などを有していてもよい。 The group R 2 is a hydrogen atom, an alkyl group having 1 to 6, preferably 1 to 4 carbon atoms, which may have a branch, especially a methyl group or an ethyl group; Or an acetyl group; or a phenylalkyl group, and a fuunylalkyl group is a substituent such as a halogen atom, a lower alkyl group. It may have a kill group or the like.
基 Qはナフタレン核上に置換基を有してもよいことを意味し、 Qは炭素 原子数 1〜6、 好ましくは 1〜4の分岐を有していてもよいアルキル基、 特にメチル基、 ェチル基；炭素原子数 1〜6、 好ましくは 1〜4の分岐を 有していてもよいアルコキシ基、 特にメ トキシ基、 エトキシ基；ハロゲン 原子、 ニトロ基またはニトロソ基が例示される。 置換基の数 mは通常 0で あるが、 3個まで有していてもよい。 ただし、 ナフタレン核の 1位に置換 基を有することはない。 さらに、 mが 1のとき Qは 2個の縮合環のどちら に結合していてもよく、 mが 2または 3のとき Qは一方または両方の縮合 環に結合していてもよく、 また 2個の縮合環と共に環を形成していてもよ い。  The group Q means that it may have a substituent on the naphthalene nucleus, and Q is an alkyl group having 1 to 6, preferably 1 to 4 carbon atoms, which may have a branch, especially a methyl group, An ethyl group; an alkoxy group having 1 to 6, preferably 1 to 4 carbon atoms which may have a branch, especially a methoxy group, an ethoxy group; a halogen atom, a nitro group or a nitroso group. The number m of the substituents is usually 0, but may have up to 3. However, it does not have a substituent at the 1-position of the naphthalene nucleus. Further, when m is 1, Q may be bonded to either of the two fused rings, when m is 2 or 3, Q may be bonded to one or both fused rings, and May form a ring together with the condensed ring of the above.
本発明ァゾ化合物は、 一般式 [II]で表される芳香族アミン類を亜硝酸ナ トリウムなどでジァゾ化して得られるジァゾ化合物を上記 2—ヒ ドロキシ ナフタレン一 3 , 6—ジカルボン酸およびその誘導体（例えばカルボキシァ ミ ドまたはカルボキシゥレイ ドまたはエステル）でカップリングすること により得られる。  The azo compound of the present invention is a diazo compound obtained by diazotizing an aromatic amine represented by the general formula [II] with sodium nitrite or the like to obtain the 2-hydroxynaphthalene-1,3,6-dicarboxylic acid and It can be obtained by coupling with a derivative (for example, carboxyamide or carboxyperide or ester).
さらに、 Rまたは R'が水酸基のときは適当な金属塩、 例えば C a、 B a、 M n、 S tなどの塩でレーキ化することにより得られる。  Further, when R or R 'is a hydroxyl group, it can be obtained by lake formation with an appropriate metal salt, for example, a salt of Ca, Ba, Mn, St or the like.
芳香族ァミン類、 即ち、 ァゾ基において Zを構成する化合物としては、 了二リ ン ( Zがフエニル基） 、 ひ一または^—ナフチルァミン （Zがナフ チル基） 、 モノアミノアントラセン.（Zがアンスリル基） 、 モノアミノィ ンデン （Zがインデニル基） 、 モノアミノフルォレノン （Zがフルォレニ ル基） などのモノアミノ縮合多環式炭化水素類、 モノアミノインドール （Z がインドリル基） 、 モノアミノべンゾチオフヱン （ Zがベンゾチォニル基） 、 モノアミノキノリン （Zがキノリニル基） 、 モノアミノカルバゾール （Z がカルバゾリル基） などが例示される。 これらの芳香族アミン類は置換基 を有していてもよく、 置換基としてはハロゲン、 低級アルキル、 とくにメ チル、 シァノ、 ニトロ、 低級アルコキシ基、 アミ ド基、 スルホニル基、 ァ ルキルアミノスルホニル基、 ァミノカルボニル基、 フヱノキシ基、 アルコ キシカルボニル基、 ヒ ドロキシ基、 ベンゾィルァミノ基などが例示される c 特に好ましい芳香族ァミン類は置換基を有してもよいァニリン類 （Zが フエニル基） または置換基を有していてもよい α—または /3—ナフチルァ ミン類 （Ζがナフチル基） である。 Aromatic amines, that is, compounds constituting Z in the azo group include Rinylin (Z is a phenyl group), Hiichi or ^ -naphthylamine (Z is a naphthyl group), monoaminoanthracene. Is an anthryl group), monoaminoindene (Z is an indenyl group), monoamino condensed polycyclic hydrocarbons such as monoaminofluorenone (Z is a fluorenyl group), monoaminoindole (Z is an indolyl group), monoaminobenzodithiophene (Z is benzothionyl group), monoaminoquinoline (Z is quinolinyl group), monoaminocarbazole (Z Is a carbazolyl group). These aromatic amines may have a substituent. Examples of the substituent include halogen, lower alkyl, especially methyl, cyano, nitro, lower alkoxy, amide, sulfonyl, and alkylaminosulfonyl groups. , § amino carbonyl group, Fuwenokishi group, an alkoxycarbonyl group, arsenate Dorokishi group, c particularly preferred aromatic Amin compounds etc. Benzoiruamino groups are exemplified good Anirin acids have a substituent (Z is phenyl group) or Α- or / 3-naphthylamines (Ζ is a naphthyl group) which may have a substituent.
アミン類からジァゾ化合物を得る方法は特に限定的ではない。 芳香族第 1級ァミ ン類を亜硝酸ナトリウムでジァゾ化する一般的方法を使用すれば よい。  The method for obtaining the diazo compound from the amines is not particularly limited. A general method for diazotizing aromatic primary amines with sodium nitrite may be used.
ジァゾ化合物はさらに前述の 2—ヒ ドロキシナフタレン一 3 , 6—ジカ ルポキシアミ ド、 カルボキシゥレイ ドまたはエステルでカツプリングする がこの方法も常套の方法を採用すればよい。 - 本発明ァゾ化合物は顔料、 印刷インキ、 塗料、 高分子材料用練り込み着 色料などに使用できる。  The diazo compound is further coupled with the above-mentioned 2-hydroxynaphthalene-13,6-dicaroxyamide, carboxyperide or ester, and a conventional method may be employed. -The azo compound of the present invention can be used for pigments, printing inks, paints, kneading coloring materials for polymer materials, and the like.
以下、 実施例をあげて説明する。  Hereinafter, an example will be described.
実施例 1 Example 1
2 -ヒ ドロキシー 1—( 2 '—メチル一 5 '—二トロフエ二ルァゾ）一 3， 6—ビスフヱニルアミノカルボ二ルナフタレンの合成  Synthesis of 2-Hydroxy 1- (2'-methyl-1 5'-nitrophenylazo) -1,3,6-bisphenylaminocarbonylnaphthalene
[ IV ]
Figure imgf000010_0001
/03637 [IV]
Figure imgf000010_0001
/ 03637
ァミン成分として 2—メチルー 5—ニトロァニリン 4.6 gを水 100 gに懸濁し、 35%—塩酸 4.0 gを加えて溶解する。 その後、 0°Cに保 ちながら亜硝酸ナトリウム 2.3 gを水 10 gに溶解した溶液を滴下して ジァゾ化を行う。 他方、 カップラ一成分として 2—ヒ ドロキシー 3， 6— ビスフエニルァミノカルボ二ルナフタレン 9.6 gをメタノール 190g に懸濁し、 水酸化ナトリウム 2.0 gを水 10 gに溶解した溶液を添加し、 溶解した後、 15°Cに保つ。 これに上述のジァゾ溶液を約 20分で添加し てカップリング反応を行う。 さらに 30分撹拌後、 水 100 gを加え、 7 0°Cに昇温し、 水 600 gを約 1時間かけて滴下する。 その後、 徐冷して 室温にて吸引濾過する。 生成物をメタノールで超音波洗浄した後、 減圧下 乾燥して、 明るい黄み赤色粉末〔2—ヒ ドロキシー 1一（2'—メチルー 5' 一二トロフエニルァゾ）一 3， 6―ビスフエニルァミノカルボニルナフタレ ン〕 8.2 gを得た（融点♦分解点： 331.2°C (分解)）。 4.6 g of 2-methyl-5-nitroaniline as an amine component is suspended in 100 g of water and dissolved by adding 4.0 g of 35% hydrochloric acid. Thereafter, a solution prepared by dissolving 2.3 g of sodium nitrite in 10 g of water is added dropwise while maintaining the temperature at 0 ° C, and diazotization is performed. On the other hand, 9.6 g of 2-hydroxy-3,6-bisphenylaminocarbonylnaphthalene as a component of the coupler was suspended in 190 g of methanol, and a solution prepared by dissolving 2.0 g of sodium hydroxide in 10 g of water was added. After that, keep at 15 ° C. To this, the above-mentioned diazo solution is added in about 20 minutes to perform a coupling reaction. After stirring for another 30 minutes, 100 g of water is added, the temperature is raised to 70 ° C, and 600 g of water is added dropwise over about 1 hour. Thereafter, the mixture is gradually cooled and suction-filtered at room temperature. The product is ultrasonically washed with methanol and dried under reduced pressure to give a bright yellowish red powder [2-hydroxy-11- (2'-methyl-5'-12-trophenylazo) -1,3-bisphenylamino]. Carbonyl naphthalene] 8.2 g was obtained (melting point ♦ decomposition point: 331.2 ° C (decomposition)).
この赤外吸収スぺク トル（KB r法）を第 1図に示す。  This infrared absorption spectrum (KBr method) is shown in FIG.
実施例 1で得たァゾ化合物、 市販品である 2—ヒ ドロキシー 3—フエ二 ルァミノカルボニル誘導体 (比較例 1)、 および特開平 2— 302471に 記載の 2—ヒドロキシ— 6—フヱニルァミノカルボニル誘導体（比較例 2) についての、 耐水性、 耐薬品性、 耐溶剤性、 耐移行性および焼付塗料とし ての耐光性等の諸性質を第 1表に示す。 The azo compound obtained in Example 1, a commercially available 2-hydroxy-3-phenylaminocarbonyl derivative (Comparative Example 1), and 2-hydroxy-6-phenyl described in JP-A-2-302471 Table 1 shows properties of the aminocarbonyl derivative (Comparative Example 2), such as water resistance, chemical resistance, solvent resistance, migration resistance, and light resistance as a baking paint.
Figure imgf000012_0001
Figure imgf000012_0001
耐水性、 耐薬品性、 耐溶剤性は次のようにして評価した。 Water resistance, chemical resistance, and solvent resistance were evaluated as follows.
耐水性：試料 1部を水 20部に加え、 超音波で 20分間分散させる。 煮 沸 1分後、 冷却濾過し、 濾液の色を観察し、 以下に示す A〜Eに従って評 価した。  Water resistance: Add 1 part of sample to 20 parts of water and disperse by ultrasonic wave for 20 minutes. One minute after boiling, the mixture was filtered under cooling, the color of the filtrate was observed, and evaluation was performed according to A to E shown below.
耐薬品性：試料 1部を塩酸または水酸化ナトリゥムそれぞれの 5 %水溶 液 20部に加え、 超音波で 5分間分散させる。 濾過後、 濾液の色を観察し、 以下の A〜Eに従って評価した。  Chemical resistance: Add 1 part of sample to 20 parts of 5% aqueous solution of hydrochloric acid or sodium hydroxide, and disperse by ultrasonic wave for 5 minutes. After filtration, the color of the filtrate was observed and evaluated according to the following A to E.
耐溶剤性：試料 1部をアセトンまたはメタノールまたはキシレン 20部 に加え、 超音波で 5分間分散させる。 濾過後、 濾液の色を観察し、 以下に 示す A~Eに従って評価した。  Solvent resistance: Add 1 part of sample to 20 parts of acetone, methanol or xylene and disperse by ultrasonic wave for 5 minutes. After filtration, the color of the filtrate was observed and evaluated according to A to E shown below.
全く着色が認められない A  No coloring A
着色が極めてわずかである B  B with very slight coloring
着色が少しある C  C with some coloring
着色がある D  Colored D
着色が著しい E 耐移行性は、 次のようにして評価した。  E The migration resistance, which is markedly colored, was evaluated as follows.
1) 軟質ポリ塩化ビニル 100部、 ジォクチルフタレ一ト 50部、 スズマ レート 2部、 カルシウムステアレート 0.4部、 バリウムステアレート 0. 6部からなるコンパウンド 100部に対し、 試料 1部を添加し、 二本口一 ル機にて 140°C、 5分間混練した後、 100 k g ί Zcm2で加圧し、 厚さ lmmの試験片を得る。 1) 1 part of a sample was added to 100 parts of a compound consisting of 100 parts of soft polyvinyl chloride, 50 parts of octyl phthalate, 2 parts of stanmalate, 0.4 part of calcium stearate and 0.6 part of barium stearate. After kneading at 140 ° C for 5 minutes in a mouth mill, pressurize at 100 kgίZcm 2 to obtain a lmm thick test piece.
2) 1で得た試験片を 4 Ommx 50mmに切る。  2) Cut the test piece obtained in 1 into 4 Ommx 50mm.
3) 1で用いたコンパウンド 100部とホワイ トチタン 5部を 1と同様に 加工し、 4 Ommx 6 Ommに切る。 4) 3のシート上に 2の試験片を片端を合わせて重ね、 l O O g fZcm 2になるように加重する。 3) Process 100 parts of the compound used in 1 and 5 parts of white titanium in the same way as 1 and cut into 4 Omm x 6 Omm. 4) Overlap the test piece of 2 with one end on the sheet of 3 and weight it to lOO g fZcm 2 .
5) 4を 70°Cで 24時間放置する。 チタンホワイ トシ一卜への色の移行 の程度を評価する。  5) Leave 4 at 70 ° C for 24 hours. Evaluate the degree of color transfer to the titanium white sheet.
移行性なし A  No migration A
移行性やや有り B  There is some migration B
移行性有り C  Migrating C
移行性かなり有り D 焼付塗料としての耐光性は、 次のように評価した。  There is considerable migration. D The light resistance as a baking paint was evaluated as follows.
1)試料 1.0部、 ジォクチルフタレート 0.7部、 ヒマシ油 0.7部をフ 一バー式マーラーで混練 （100回転 X 3回） する。  1) Knead 1.0 part of sample, 0.7 parts of octyl phthalate, and 0.7 parts of castor oil with a fiber muller (100 rotations x 3 times).
2) 1で混練したもの 1.0部に、 硬化剤べッコゾ一ル （ER— 3653 -60) 10.0部、 ナフテン酸マンガン 0.1部を加え、 ヘラを用いガラ ス板上でよく練る。  2) To 1.0 part of the mixture kneaded in 1), add 10.0 parts of hardener bekkozol (ER-3653-60) and 0.1 part of manganese naphthenate, and knead well on a glass plate using a spatula.
3) 2で得られた試料を、 鉄板にアプリケーターを用いて 0.5m i 1 (1 .27x 10— 5m) に塗りつけた後、 通風乾燥機で 145°C、 30分間加 熱し、 焼付塗料の試験片を得る。 The sample obtained in 3) 2, after smeared 0.5mi 1 (1 .27x 10- 5 m ) using an applicator to an iron plate, heated 145 ° C, pressurized for 30 minutes at air dryer, the test of baking coating Get a piece.
4) 3の試験片を半分マスクした後、 フユザ一メーター （島津製作所製： サンテスター XF— 180 ·キセノンランプ） で 100時間照射する。 マ スクした部分としていない部分をそれぞれ測定し、 両者の色差△£により 評価する。  4) After half-masking the test piece of 3 above, irradiate it with a fuser meter (Shimadzu: Suntester XF-180 xenon lamp) for 100 hours. The masked portion and the non-masked portion are each measured, and the color difference between the two is evaluated.
△E=2以下 A  △ E = 2 or less A
△E=2〜3 B  △ E = 2〜3 B
△E=3〜5 C P /JP97/03637 △ E = 3〜5 C P / JP97 / 03637
△E=5〜8 D △ E = 5 ~ 8 D
△E=8以上 E 実施例 2  ΔE = 8 or more E Example 2
2—ヒ ドロキン一 1一 （2'—メチル一5'—ニトロフヱニルァゾ） 一 3, 6—ビス （2'—メチルフヱニルァミノカルボニル） ナフタレンの合成  Synthesis of 2-hydroquinone-1-1 (2'-methyl-5'-nitrophenylazo) -1,3,6-bis (2'-methylphenylaminocarbonyl) naphthalene
Figure imgf000015_0001
Figure imgf000015_0001
カップラー成分として実施例 1の 2—ヒ ドロキシ一 3， 6—ビスフエ二 ルアミノカルボ二ルナフタレンを 2—ヒ ドロキシー 3, 6—ビス （2'—メ チルフヱニルァミノ力ルポニル） ナフタレン 14. 3 gに代えることの他 は、 実施例 1と同様にして、 黄み赤色粉末〔2—ヒ ドロキシー 1— (2'— メチルー 5'—ニトロフエニルァゾ） 一3， 6—ビス （2'—メチルフエ二 ルァミノカルボニル） ナフタレン〕 9.2 gを得た （融点 ·分解点： 307. 0°C (分解） ） 。 As a coupler component, 2-hydroxy-1,3,6-bisphenylaminocarbonylnaphthalene of Example 1 was replaced with 2-hydroxy-3,6-bis (2'-methylphenylaminoaminopropyl) naphthalene 14.3 A yellowish red powder [2-hydroxy-1- (2'-methyl-5'-nitrophenylazo) -1,3,6-bis (2 ') was obtained in the same manner as in Example 1 except that g was replaced with g. —Methylphenylaminocarbonyl) naphthalene 9.2 g (melting point / decomposition point: 307.0 ° C. (decomposition)).
実施例 3 , Example 3,
2-b Κπキシ一 1一 （2，一メチル一 5'—二トロフエニルァゾ) - 3 , 6—ビス （2'—メ トキシフエニルァミノカルボニル） ナフタレンの合成 [VI]
Figure imgf000016_0001
カップラー成分として実施例 1の 2—ヒドロキシ 3, 6—ビスフヱニル ァミノカルボ二ルナフタレンを、 2—ヒドロキシ一 3, 6—ビス （2， 一 メ トキシフエニルァミノカルボニル） ナフタレン 15. 1 gに代えること の他は、 実施例 1と同様にして、 青み赤色粉末〔2—ヒ ドロキシー 1一 （2 '—メチル一 5'—二トロフエニルァゾ） 一3, 6—ビス （2'—メ トキシフエ ニルァミノカルボニル） ナフタレン〕 9. 4gを得た （融点 ·分解点： 2 93. 5°C (分解） ） 。 Synthesis of 2-b Κπxy-1-1 (2,1-methyl-1-5'-ditrophenylazo) -3,6-bis (2'-methoxyphenylaminocarbonyl) naphthalene [VI]
Figure imgf000016_0001
Substituting 15.1 g of 2-hydroxy-1,6-bis (2,1-methoxyphenylaminocarbonyl) naphthalene for 2-hydroxy-3,6-bisphenylaminocarbonylnaphthalene of Example 1 as a coupler component Other than the above, in the same manner as in Example 1, a bluish red powder [2-hydroxy-11- (2'-methyl-1-5'-nitrophenylazo) -1,3,6-bis (2'-methoxyphenylaminocarbonyl) Naphthalene] 9.4 g was obtained (melting point / decomposition point: 293.5 ° C (decomposition)).
実施例 4 Example 4
—ヒ―ド口キシー 1— (2'—メ トキシ一 5'—フエニルァミノ力ルポ二 ルフエ二ルァゾ） 一 3， 6—ビスフエニルァミノカルボ二ルナフタレンの 合成  —Head mouth xylene 1— (2'-Methoxy-5'-phenylaminophenol-1) Synthesis of 3,6-bisphenylaminocarbonylnaphthalene
Figure imgf000016_0002
Figure imgf000016_0002
アミン成分として実施例 1の 2—メチル—5—二トロアニリンを、 2 メ トキシ一 5—フエニルァミノカルボ二ルァニリン 7. 3 gに代えて、 こ れを水 5 O gとメタノール 50 gに懸濁させることの他は、 実施例 1と同 様にして、 青み赤色粉末〔2—ヒドロキシ _1一 （2，ーメ トキシ一 5'— フエニルァミノカルボニルフヱニルァゾ） 一3, 6—ビスフヱニルァミノ カルボ二ルナフタレン〕 6. 8 gを得た （融点 ·分解点： 282.5°C (分 解） ） 。 As the amine component, 2-methyl-5-nitroaniline of Example 1 was used. The same procedure as in Example 1 was repeated except that methoxy-5-phenylaminocarbonylaniline was used instead of 7.3 g and suspended in 50 g of water and 50 g of methanol. 6.8 g of red powder [2-hydroxy_1- (2, -methoxy-5'-phenylaminocarbonylphenylazo) -1,6-bisphenylaminocarbonylcarbonylnaphthalene] Obtained (melting point / decomposition point: 282.5 ° C (decomposition)).
実施例 5〜 22 Examples 5 to 22
アミン成分として実施例 1の 2—メチル一5—ニトロァニリンを、 第 2 表に示すァミンに代えて、 これを水 50 gとメタノール 50 gに懸濁させ ること、 およびカップラー成分として 2—ヒ ドロキシ一 3， 6—ビスフエ ニルァミノカルボ二ルナフタレンを、 第 2表に示す力ップラーに代えるこ との他は、 実施例 1と同様にしてァゾ化合物を合成した。 合成したァゾ化 合物の融点 ·分解点を第 2表に示す。 The 2-amine-5-nitroaniline of Example 1 was used as the amine component instead of the amine shown in Table 2 and suspended in 50 g of water and 50 g of methanol, and 2-hydroxy was used as the coupler component. An azo compound was synthesized in the same manner as in Example 1 except that 1,3,6-bisphenylaminocarbonylnaphthalene was replaced with a force puller shown in Table 2. Table 2 shows the melting points and decomposition points of the synthesized azo compounds.
第 2表 Table 2
Figure imgf000018_0001
Figure imgf000018_0001
16 16
差替え用紙 （規貝 IJ26) 2表（つづき） Replacement paper (Kaikai IJ26) 2 tables (continued)
Figure imgf000019_0001
Figure imgf000019_0001
17 17
差替え用紙 （規則 26) 第 2表（つづき） Replacement form (Rule 26) Table 2 (continued)
Figure imgf000020_0001
Figure imgf000020_0001
18 18
差替え用紙 （規貝 IJ26) 2表 （つづき） 融点 ァミン (上 s) / 力ヅフ。ラー (下段） ァゾ化合物の構造式 色合い Replacement paper (Kaikai IJ26) Table 2 (continued) Melting point amine (top s) / force. (Lower) Structural formula of azo compound
分解点  Decomposition point
4-ク卯- 2-メチルァ二リン [ X X 4-Ku- 2-Methylaniline [X X
266.6'C 黄みの赤 266.6'C yellowish red
(融解） (Melting)
2-ヒト * Dキシ- 3, 6- ス (2' -ェトキシ- フ;^ルァミノカルホ -、;：ル)ナフ外ン2-Human * D-xy-3,6-s- (2'-ethoxy-;; L-aminocarbo-,;: le)
Figure imgf000021_0001
Figure imgf000021_0001
4-ク DD-2-メトキシァニリン 暗い 328.9*0 青みの赤 (分解）, 6- ス ( ン、尸イミタ"、尸 Dン -5-ィル- [ 4-ku DD-2-methoxyaniline dark 328.9 * 0 bluish red (decomposed), 6-
ァミノカルホ'ニル) -2-ヒドロキシナフタレン 2-aminonaphthalene
Figure imgf000021_0002
Figure imgf000021_0002
2-メチル -5-二ト!]ァニリン 暗い 334.6eC 茶色みの紫 <分解）, 6-ヒ *ス（ ン、尸イミタ *、尸 Dン- 5-ィル- アミ カルホ'ニル) - 2 -ヒド Dキシナフタレン2-Methyl-5-di!] Aniline dark 334.6 e C brownish purple <decomposition), 6-hys * (n, sodium imita *, sodium D-5-yl-ami-carbo'nil)- 2-Hyd D xinaphthalene
Figure imgf000021_0003
Figure imgf000021_0003
2-メチル -5-ニト Dァニリン 明るい 239. *C 茶色みの赤 (分解）2-Methyl-5-nitro Daniline Bright 239. * C Brownish red (decomposed)
2-ヒド Dキシ -3, 6- ス (2' -ク DD- フエニルウレ仆 *カルホ'ニル)ナフタレン2-Hyd Dxy -3,6-s (2'-D DD-Phenylurei * Carpho'nyl) naphthalene
Figure imgf000021_0004
Figure imgf000021_0004
19 19
差替え用紙 （規則 26) 第 2表 （つづき） Replacement form (Rule 26) Table 2 (continued)
Figure imgf000022_0001
Figure imgf000022_0001
2—ヒドロキシ一 3 , 6—ジヒドロキシカルボ二ルー (4'—メチル 一 2'—スルホン酸フヱニルァゾ） ナフタレンのカルシウム塩の合成 Synthesis of Calcium Salt of 2-Hydroxy-1,3,6-dihydroxycarbonyl (4'-methyl-1 2'-phenylazosulfonic acid) naphthalene
Figure imgf000023_0001
Figure imgf000023_0001
4—ァミノ トルエン一 3—スルホン酸 （4Β— Ac i d) 5.0 gを水 250 gに分散させ、 35%—塩酸 5.4 gを加えて溶解する。 その後、 0°Cに保ちながら亜硝酸ナトリウム 2.1 gを水 10 gに溶解した溶液を 約 20分かけて滴下してジァゾ化を行う。 他方、 2—ヒ ドロキシー 3， 6 ージヒドロキシカルボ二ルナフタレン 6. 4 gを N—メチル一 2—ピロリ ドン 200 gおよび水 200 gに懸濁し、 10%—水酸化ナトリウム水溶 液 38.5 g、 および 5 %—ロジン溶液 24. 0 gを添加し、 溶液させた 後、 13 (±2) °Cに保つ。 これに上述のジァゾ溶液を約 30分で滴下し、 さらに 90分撹拌する。 反応液の pHを 9.0〜9.5に調整した後、 この 溶液を塩化カルシウム二水和物 6.7 gを水 125 gに溶解した溶液に滴 下し、 レーキ化する。 30分後、 70°Cに昇温し、 30分程放置した後、 室温まで徐冷し、 水 200 gを加え、 吸引濾過した。，生成物を水洗して乾 燥すると、 濃い赤色粉末〔2—ヒドロキシー 3, 6—ジヒドロキシカルボ二 ル一 1— (4'一メチル一 2'—スルホン酸フエニルァゾ） ナフタレンの力 ルシゥム塩〕 10.3 gを得た （融点 ·分解点： 406.1°C (分解） ） 。 この赤外吸収スぺク トル （KB r法） を第 2図に示す。 1一 （5 '—クロ口一 4'—メチル一2'—スルホン酸フエニルァゾ） 一 2—ヒ ドロキシー 3 , 6—ジヒ ドロキシカルボニルナフタレンのカルシゥ ム塩の合成 5.0 g of 4-aminotoluene-3-sulfonic acid (4Β-Acid) is dispersed in 250 g of water, and dissolved by adding 5.4 g of 35% hydrochloric acid. Then, while maintaining the temperature at 0 ° C, a solution prepared by dissolving 2.1 g of sodium nitrite in 10 g of water is added dropwise over about 20 minutes to perform diazotization. On the other hand, 6.4 g of 2-hydroxy-3,6-dihydroxycarbonylnaphthalene was suspended in 200 g of N-methyl-1-pyrrolidone and 200 g of water, and 38.5 g of a 10% aqueous solution of sodium hydroxide, and Add 24.0 g of 5% rosin solution, dissolve, and keep at 13 (± 2) ° C. The above diazo solution is added dropwise to the mixture in about 30 minutes, and the mixture is further stirred for 90 minutes. After adjusting the pH of the reaction solution to 9.0 to 9.5, this solution is added dropwise to a solution of 6.7 g of calcium chloride dihydrate in 125 g of water for lake formation. Thirty minutes later, the temperature was raised to 70 ° C., left for about 30 minutes, gradually cooled to room temperature, 200 g of water was added, and suction filtration was performed. The product is washed with water and dried to give a dark red powder [2-hydroxy-3,6-dihydroxycarbone-1-1- (4'-methyl-1-2'-phenylazo-sulfonate) The power of naphthalene Lucidium salt] 10.3 g (Melting point · decomposition point: 406.1 ° C (decomposition)). Fig. 2 shows this infrared absorption spectrum (KBr method). Synthesis of calcium salt of 11- (5'-chloro-1-4'-methyl-12'-phenylazosulfonic acid) 1-2-hydroxy-3,6-dihydroxycarbonylnaphthalene
Figure imgf000024_0001
実施例 23の 4—ァミ ノ トルエン一 3—スルホン酸 （4 B— A c i d) を、 4—ァミノ一 2—クロ口 トルエン一 5—スルホン酸 （2B— Ac i d) 5.9 gに代えることの他は、 実施例 23と同様にして、 濃い赤色粉末 〔1 一 （5'—クロロー 4'—メチル一2'—スルホン酸一フヱニルァゾ） 一2 -ヒ ドロキシ一 3, 6—ジヒ ドロキシカルボ二ルナフタレンのカルシウム 塩〕 11.3 gを得た （融点 ·分解点： 446.7°C (分解） ） 。
Figure imgf000024_0001
Substituting 5.9 g of 4-amino-12-chlorotoluene-5-sulfonic acid (2B-Acid) for 4-aminotoluene-3-sulfonic acid (4B-Acid) in Example 23 Otherwise, in the same manner as in Example 23, dark red powder [1-1 (5'-chloro-4'-methyl-12'-monophenylazosulfonic acid) -1,2-hydroxy-1,3,6-dihydroxycarbonylnaphthalene Calcium salt] 11.3 g was obtained (melting point / decomposition point: 446.7 ° C (decomposition)).
実施例 25 Example 25
(1) 2—ヒ ドロキシ一 3， 6—ビス（2'—ピリ ジルアミノカルボニル) ナフタレンの合成  (1) Synthesis of 2-hydroxy-1,3,6-bis (2'-pyridylaminocarbonyl) naphthalene
Figure imgf000024_0002
2—ヒ ドロキシー 3, 6—ジヒドロキシカルボ二ルナフタレン 14.3 g および 2—アミノビリジン 13.6 gを、 N—メチルー 2—ピロリ ドン 1 20 gおよび酢酸ェチル 150 gに溶解し、 これにジシクロへキシルカル ボジィミ ド 30.9 gを加え、 室温で約 15時間反応する。 不溶物を濾去 した後、 濾液を約半分の重量まで濃縮し、 次いでジグライム 30.6 gを 加え、 170°Cに昇温する。 2時間後、 室温まで冷却し、 不溶物を濾去す る。 濾液を濃縮した後、 酢酸ェチル 200 gを加え、 超音波処理して析出 した結晶を濾過する。 生成物を乾燥すると、 黄白色結晶 〔2—ヒ ドロキシ 一 3， 6—ビス（2'—ピリジルァミノカルボニル）ナフタレン〕 15.7 g を得た（融点： 311.2°C)。
Figure imgf000024_0002
Dissolve 14.3 g of 2-hydroxy-3,6-dihydroxycarbonylnaphthalene and 13.6 g of 2-aminoviridine in 120 g of N-methyl-2-pyrrolidone and 150 g of ethyl acetate, and add dicyclohexylcarbodiimide. Add 30.9 g and react at room temperature for about 15 hours. After filtering off the insoluble matter, the filtrate is concentrated to about half the weight, then 30.6 g of diglyme is added, and the temperature is raised to 170 ° C. After 2 hours, cool to room temperature and filter off insolubles. After concentrating the filtrate, add 200 g of ethyl acetate, and sonicate and filter the precipitated crystals. The product was dried to obtain 15.7 g of yellowish white crystals [2-hydroxy-13,6-bis (2'-pyridylaminocarbonyl) naphthalene] (melting point: 311.2 ° C).
(2) 2—ヒ ドロキシー 1— (5'—ジェチルアミノスルホニルー 2'— メ トキシフヱニルァゾ） 一 3 , 6—ビス （ 2 '—ピリジルァミノ力ルポニル) ナフタレンの合成  (2) Synthesis of 2-hydroxy 1- (5'-Jetylaminosulfonyl-2'-methoxyphenylazo) 1-3,6-bis (2'-pyridylaminoaminopropyl) naphthalene
Figure imgf000025_0001
Figure imgf000025_0001
アミン成分として実施例 1の 2—メチル一5—ニトロァニリンを、 5— ジェチルアミノスルホニル一 2—メ トキシァニリン 7. 8 gに代えて、 こ れを水 50 gとメタノール 50 gに懸濁させること、 および力ップラー成 分として 2—ヒ ドロキシー 3， 6—ビスフエニルアミノカルボ二ルナフタ レンを、 前記 （1) で合成した 2—ヒ ドロキシ一 3, 6—ビス （2'—ピリ ジルァミノカルボニル） ナフタレン 9. 6 gに代えることの他は、 実施例 1と同様にして、 茶色み赤色である 〔2—ヒ ドロキシー 1— (5'—ジェ チルアミノスルホニル一 2'—メ トキシフヱニルァゾ） 一3, 6—ビス （2 '—ピリジルァミノカルボニル） ナフタレン〕 7. l gを得た （融点 ·分 解点： 197. 6°C (分解） ） 。 Instead of 2-methyl-1,5-nitroaniline of Example 1 as 7.8 g of 5-methylethylsulfonyl-12-methoxyaniline as an amine component, this was suspended in 50 g of water and 50 g of methanol. , And 2-hydroxy-3,6-bisphenylaminocarbonylnaphthalene as a Wippler component were synthesized using the 2-hydroxy-1,3,6-bis (2'-pyri) synthesized in (1) above. (2-Hydroxy-1- (5'-ethylaminosulfonyl-1 2'-medium), which is brownish-red in the same manner as in Example 1 except that 9.6 g of ziraminocarbonyl) naphthalene is used. Toxylphenylazo) -1,6-bis (2'-pyridylaminocarbonyl) naphthalene] 7. lg was obtained (melting point / resolving point: 197.6 ° C (decomposition)).
実施例 26 Example 26
2—ヒ ドロキシ 3, 6—ビス（チアゾ一ル一 2'—ィルァミノカルボニル) ナフタレンの合成  Synthesis of 2-Hydroxy 3,6-bis (thiazolyl-2'-ylaminocarbonyl) naphthalene
Figure imgf000026_0001
Figure imgf000026_0001
2—了ミノチアゾ一ル 6.3 gを N—メチル一2—ピロリ ドン 50.0 g およびトルエン 30.0 gに溶解し、 60°Cに加熱する。 これに 2—ヒ ド 口キシ一 3， 6—ビスクロロカルボ二ルナフタレン 5.6 gを N—メチル一 2—ピロリ ドン 120.0 gに溶解した溶液を添加し、 80°Cに昇温する。 約 24時間後、 濃縮し、 水 470 gを加える。 析出した結晶を濾過し、 メ タノールて洗浄後、 乾燥して肌色結晶 〔2—ヒ ドロキシ一 3, 6—ビス（チ ァゾール一 2'—ィルァミノカルボニル）ナフタレン〕 1.7 gを得た（融点 ： 286.6°C)o Dissolve 6.3 g of 2-aminothiazol in 50.0 g of N-methyl-1-pyrrolidone and 30.0 g of toluene and heat to 60 ° C. To this is added a solution of 5.6 g of 2-hydroxy-3-, 6-bischlorocarbonylnaphthalene dissolved in 120.0 g of N-methyl-12-pyrrolidone, and the temperature is raised to 80 ° C. After about 24 hours, concentrate and add 470 g of water. The precipitated crystals were filtered, washed with methanol, and dried to obtain 1.7 g of flesh-colored crystals [2-hydroxy-1,3,6-bis (thiazole-1 2'-ylaminocarbonyl) naphthalene] (melting point). : 286.6 ° C) o
実施例 27 Example 27
(1) 2—ヒ ドロキシ一 3, 6—ビス（ベンゾチアゾ一ルー 2'—ィルァ ミノカルボニル）ナフタレンの合成
Figure imgf000027_0001
実施例 26の 2—ァミノチアゾールを 2—ァミノベンゾチアゾール 9. 4gに代えることの他は、 実施例 26と同様にして、 肌色結晶〔2—ヒド 口キシ一 3， 6 -ビス（ベンゾチアゾールー 2'—ィルァミノカルボニル）ナ フタレン〕 1. 9 gを得た（融点： 364.1°C)。 (1) Synthesis of 2-hydroxy-1,3,6-bis (benzothiazo-l-2'-ylaminocarbonyl) naphthalene
Figure imgf000027_0001
Except that 9.4 g of 2-aminothithiazole was used in place of 2-aminothiazole in Example 26, the same procedure as in Example 26 was carried out to give a flesh-colored crystal [2-Hydroxoxy-1,3,6-bis (benzo). Thiazole-2'-ylaminocarbonyl) naphthalene] 1.9 g was obtained (melting point: 364.1 ° C).
(2) 2—ヒ ドロキシ一 1一 （2，ーメ トキシ一 5'—フヱニルァミノカル ボニルフェニル） ァゾー 3, 6—ビス （ベンゾチアゾール一 2 "—ィルァ ミノカルボニル） ナフタレンの合成  (2) Synthesis of 2-hydroxy-1- (2, -methoxy-5'-phenylaminocarbonylcarbonyl) azo-3,6-bis (benzothiazole-1 "-ylaminocarbonyl) naphthalene
Figure imgf000027_0002
Figure imgf000027_0002
アミン成分として、 2—メ トキシ一 5—フエニルアミノカルボ二ルァニ リン 1.46 gを、 水 20 gに懸濁し、 35%—塩酸 1.8 gを加える。 そ の後、 0°Cに保ちながら亜硝酸ナトリウム 0.84 gを水 5 gに溶解した 溶液を滴下してジァゾ化を行う。 その後、 ホウフッ化水素酸 4 gを加え、 析出するジァゾ二ゥム塩を濾過する。 他方、 カップラー成分として、 2—ヒドロキシ一 3， 6—ビス （ベンゾ チアゾ一ル一 2'—ィルァミノカルボニル） ナフタレン 1. 19gを N— メチル一 2—ピロドリン 20 gに溶解し、 さらにナトリウムメ トキシド 0.As an amine component, 1.46 g of 2-methoxy-5-phenylaminocarbonylaniline is suspended in 20 g of water, and 1.8 g of 35% hydrochloric acid is added. Then, while maintaining the temperature at 0 ° C, a solution of 0.84 g of sodium nitrite dissolved in 5 g of water is added dropwise to perform diazotization. Thereafter, 4 g of borofluoric acid is added, and the precipitated diazodium salt is filtered. On the other hand, as a coupler component, 1.19 g of 2-hydroxy-1,6-bis (benzothiazolyl-2'-ylaminocarbonyl) naphthalene was dissolved in 20 g of N-methyl-12-pyrrolidine, and sodium Toxide 0.
25 gを加え、 溶解した後、 15°Cに保つ。 これに上述のジァゾ二ゥム塩 を N—メチル—2—ピロリ ドン 15 gに溶解した溶液を約 20分で添加し てカップリング反応を行う。 さらに 1時間以上撹拌した後、 酢酸 0.22 gを添加し、 続いてメタノール 50 gをゆつく り添加する。 吸引濾過によ り、 生成物を得、 メタノールで超音波洗浄した後、 減圧下乾燥して、 暗い 赤色粉末〔2—ヒドロキシー 1— (2，ーメ トキシ一 5'—フヱニルァミノ カルボ二ルフヱニル） ァゾ一 3， 6—ビス （ベンゾチアゾ一ルー 2''—ィ ルァミノカルボニル） ナフタレン〕 1. 17 gを得た （融点 ·分解点：Add 25 g, dissolve and keep at 15 ° C. A solution prepared by dissolving the above diazodimate salt in 15 g of N-methyl-2-pyrrolidone is added thereto in about 20 minutes to perform a coupling reaction. After stirring for an additional hour or more, add 0.22 g of acetic acid, and then slowly add 50 g of methanol. The product was obtained by suction filtration, washed ultrasonically with methanol, and dried under reduced pressure to give a dark red powder [2-hydroxy-1- (2, -methoxy-5'-phenylaminocarbonylcarbinyl) α]. 1.17 g of zo-1,3,6-bis (benzothiazoyl 2 ''-ylaminocarbonyl) naphthalene (melting point / decomposition point:
316. 3°C (分解） ） 。 実施例 28 316.3 ° C (decomposition)). Example 28
(1) 2—ヒドロキシー 3, 6—ビス（4'， 5'—ジシァノィミダゾール -2'一ィルァミノカルボニル）ナフタレンの合成  (1) Synthesis of 2-hydroxy-3,6-bis (4 ', 5'-dicyanimidazole-2'-ylaminocarbonyl) naphthalene
Figure imgf000028_0001
実施例 26の 2—ァミノチアゾールを 2—ァミノ一 4 , 5—ジシァノィ ミダゾ一ル 8.3 gに代えることの他は、 実施例 26と同様にして、 肌色結晶 〔2—ヒドロキシ 3, 6—ビス（4', 5'—ジシァノィミダゾール —2'—ィルァミノカルボニル）ナフタレン〕 3.5 gを得た（融点： 256. 8。C)。
Figure imgf000028_0001
A flesh-colored crystal [2-hydroxy-3,6-bis] was prepared in the same manner as in Example 26 except that 8.3 g of 2-aminoaminothiazole in Example 26 was replaced with 8.3 g of 2-amino-4-dicyanomidazole. (4 ', 5'-dicyanimidazole —2′-ylaminocarbonyl) naphthalene] (3.5 g, melting point: 256.8.C).
(2) 2—ヒ ドロキシ一 1一 （2'—メ トキシ一 5'—フエニルアミノカ ルボニルフエニル） ァゾ -3, 6—ビス （ 4 ' ' , 5 ' '—ジシァノイミダゾ - ル— 2 ''—ィルァミノ力ルポニル） ナフタレンの合成  (2) 2-Hydroxy-1-1 (2'-Methoxy-5'-phenylaminocarbonylphenyl) azo-3,6-bis (4 '' ', 5' '-dicyanimidazo-l-2'-ylamino power Ruponyl) Synthesis of naphthalene
Figure imgf000029_0001
Figure imgf000029_0001
力ップラー成分として、 実施例 27 (2) の 2—ヒ ドロキシ一 3, 6— ビス （ベンゾチアゾールー 2'—ィルァミノカルボニル） ナフタレンを、 2—ヒドロキシ一 3， 6—ビス （4'， 5'ージシァノィミダゾ一ル一 2'— ィルァミノカルボニル） ナフタレン 1. 49 gに代えることの他は、 実施 例 27 (2) と同様にして、 暗い赤色粉末〔2—ヒ ドロキシ一 1一 （2'— メ トキシー 5'—フヱニルァミノカルボ二ルフヱニル） ァゾ一 3， 6 -ビス (4' '， 5"—ジシァノイミダゾールー 2''—ィルアミノカルボニル） ナ フタレン〕 0. 83 gを得た （融点 ·分解点： 320. 6°C (分解） ） 。 実施例 29〜 73 The 2-hydroxy-1,3,6-bis (benzothiazole-2′-ylaminocarbonyl) naphthalene of Example 27 (2) was replaced with 2-hydroxy-1,3,6-bis (4 ′, 5'-dicyanimidazole-1'-ylaminocarbonyl) naphthalene 1. A dark red powder [2-hydroxy) was prepared in the same manner as in Example 27 (2) except that 1.49 g was used. 1 1 1 (2'-Methoxy 5'-Phenylaminocarbonylphenyl) azo-1,3,6-bis (4 '', 5 "-dicyanoimidazole-2" -ylaminocarbonyl Naphthalene] 0.83 g was obtained (melting point / decomposition point: 320.6 ° C (decomposition)).
アミン成分として実施例 23の 4—アミノ トルエン一 3—スルホン酸を、 第 3表に示すァミンに代えること、 および力ップラー成分として 2—ヒ ド 口キシー 3, 6—ジヒドロキシカルボ二ルナフタレンを、 第 3表に示す力ッ ブラーに代えること、 および塩化カルシウム二水和物の使用量を 1. 1倍 ないし 1 . 2倍当量とすることの他は、 実施例 2 3と同様にァゾ化合物を 合成した。 なお、 実施例 4 0、 4 1および 4 2では、 実施例 2 3の塩化力 ルシゥムに代えて、 それぞれ塩化バリウム、 塩化ストロンチウム、 塩化マ ンガンを用いた。 合成したァゾ化合物の融点 ·分解点を第 3表に示す。 As the amine component, 4-aminotoluene-13-sulfonic acid of Example 23 was replaced with the amine shown in Table 3, and as the force-puppler component, 2-hydroxy-3,6-dihydroxycarbonyl naphthalene was used. Replace with power blebbers shown in Table 3 and use 1.1 times the amount of calcium chloride dihydrate An azo compound was synthesized in the same manner as in Example 23 except that the amount was changed to 1.2 times equivalent. In Examples 40, 41, and 42, barium chloride, strontium chloride, and manganese chloride were used in place of calcium chloride in Example 23, respectively. Table 3 shows the melting points and decomposition points of the synthesized azo compounds.
第 3表 Table 3
Figure imgf000031_0001
Figure imgf000031_0001
29 29
差替え用紙 （規則 26) 第 3表 （つづき） Replacement form (Rule 26) Table 3 (continued)
Figure imgf000032_0001
第 3表 （つづき）
Figure imgf000032_0001
Table 3 (continued)
Figure imgf000033_0001
第 3表 （つづき）
Figure imgf000033_0001
Table 3 (continued)
Figure imgf000034_0001
第 3表 （つづき）
Figure imgf000034_0001
Table 3 (continued)
Figure imgf000035_0001
（つづき）
Figure imgf000035_0001
(Continued)
Figure imgf000036_0001
第 3表 （つづき）
Figure imgf000036_0001
Table 3 (continued)
Figure imgf000037_0001
第 3表 （つづき）
Figure imgf000037_0001
Table 3 (continued)
Figure imgf000038_0001
第 3表 （つづき）
Figure imgf000038_0001
Table 3 (continued)
Figure imgf000039_0001
試験例
Figure imgf000039_0001
Test example
実施例 39、 実施例 54、 および実施例 64で得たァゾ化合物について- JIS K5101に従って印刷インキを作り、 展色した。 その色彩的データを第 4表に示す。 色彩的データとして、 JIS Z8701に示される主波長ス d、 朿 ij 激純度 P e、 明度 Yを示す。 第 4表 主波長 久ゴ 刺激純度 Pe 明 度 実施例 39 61 0 nra 58.1% 1 .5% 実施例 54 6 19 nm 47.6% 8.5% 実施例 64 645 nm 32.2% 6.8% With respect to the azo compounds obtained in Example 39, Example 54, and Example 64, a printing ink was prepared according to JIS K5101 and developed. Table 4 shows the color data. As the color data, the dominant wavelength d, the intensity of pure water P e, and the lightness Y shown in JIS Z8701 are shown. Table 4 Main Wavelength Hisago Stimulation Purity Pe Lightness Example 39 61 0 nra 58.1% 1.5% Example 54 6 19 nm 47.6% 8.5% Example 64 645 nm 32.2% 6.8%
実施例 74 Example 74
2—ヒ ドロキシー 1— (2'—メ トキシ一 5'—フエニルァミノカルボ二 ルフヱニル） ァゾー 3—メ トキシカルボニル一 6— ( 3''—二トロフエ二 ル） ァミノカルボ二ルナフタレンの合成  2-Hydroxy 1- (2'-Methoxy-5'-Phenylaminocarbonyldiphenyl) azo 3-3-Methoxycarbonyl-1 6- (3 ''-Nitrophenyl) Synthesis of Aminocarbonylnaphthalene
Figure imgf000041_0001
カップラー成分として、 実施例 27 (2) の 2—ヒ ドロキシー 3, 6— ビス （ベンゾチアゾール一 2'—ィルァミノカルボニル） ナフタレンを、 2—ヒドロキシ一 3—メ トキシカルボニル一 6— （3'—二トロフヱニル） 了ミノカルボ二ルナフタレン 1. 10 gに代えることの他は、 実施例 27 (2) と同様にして、 赤色粉末〔2—ヒ ドロキシ _1一 （2'—メ トキシ一 5'—フヱニルァミノカルボ二ルフヱニル） ァゾ一 3—メ トキシカルボ二 ルー 6— (3''—ニトロフヱニル） ァミノカルボ二ルナフタレン〕 1.44 gを得た （融点 ·分解点： 315. 8°C (分解） ） 。
Figure imgf000041_0001
As the coupler component, 2-hydroxy-3,6-bis (benzothiazole-1′-ylaminocarbonyl) naphthalene of Example 27 (2) was replaced with 2-hydroxy-13-methoxycarbonyl-1-6— (3 ′). —Nitrocarbinyl Rinocarbonylnaphthalene 1. Red powder [2-hydroxy-1- (2'-methoxy-5 ') was prepared in the same manner as in Example 27 (2) except that the amount was changed to 10 g. 1.44 g of phenyl-3-aminocarbonyl 6- (3 ''-nitrophenyl) aminocarbonylnaphthalene] was obtained (melting point, decomposition point: 315.8 ° C (decomposition) )).
実施例 75 Example 75
2——ヒ ドロキシー 1一 （2'—メ トキシ一 5'—フヱニルァミノ力ルポ二 ルフヱニル） ァゾー 3—メ トキシカルボニル一 6—ベンジルォキシカルボ 二ルナフタレンの合成
Figure imgf000042_0001
2-—Hydroxy-11- (2′-Methoxy-5′-Phenylaminoaminopropyl) azo 3-Synthesis of 3-Methoxycarbonyl-6-benzyloxycarbornaphthalene
Figure imgf000042_0001
カップラー成分として、 実施例 27 (2) の 2—ヒ ドロキシ一 3， 6— ビス （ベンゾチアゾ一ルー 2'—ィルァミノカルボニル） ナフタレンを、 2—ヒ ドロキシ一 3—メ トキシカルボ二ルー 6—ベンジルォキシカルボ二 ルナフタレン 1. 01 gに代えることの他は、 実施例 27 (2) と同様に して、 赤色粉末〔2—ヒ ドロキン一 1— (2'—メ トキシ一 5'—フヱニル ァミノカルボニルフヱニル） ァゾ一 3—メ トキシカルボ二ルー 6—べンジ ルォキシカルボ二ルナフタレン〕 1. 42 gを得た （融点 ·分解点： 33 2. 6°C (分解） ） 。  As a coupler component, 2-hydroxy-1,3,6-bis (benzothiazo-l-u 2'-ylaminocarbonyl) naphthalene of Example 27 (2) was used, and 2-hydroxy-13-methoxy-carbo-l-u 6-benzyl Red powder [2-hydroxyquinone 1- (2'-methoxy-5'-phenyl) was prepared in the same manner as in Example 27 (2) except that the carboxycarbonylnaphthalene was replaced with 1.01 g. Aminocarbonylphenyl) azo-3-methoxycarbonyl 6-benzyloxycarbonylnaphthalene] 1.42 g was obtained (melting point / decomposition point: 332.6 ° C (decomposition)).
実施例 76 Example 76
2—ヒドロキシ一 1— (2'—メ トキシ一 5 ' —フエニルァミノ力ルポ二 ルフ： Lニル） ァゾ一 3, 6—ビス （フエノキシカルボニル） ナフタレンの 合成  2-Hydroxy-1- (2'-methoxy-5'-phenylaminopropyl: Lnyl) azo-1,3,6-bis (phenoxycarbonyl) naphthalene
Figure imgf000042_0002
Figure imgf000042_0002
カップラー成分として、 実施例 27 (2) の 2—ヒドロキシ一 3, 6 ビス （ベンゾチアゾールー 2'—ィルァミノカルボニル） ナフタレンを. 2—ヒ ドロキシ一 3， 6—ビス （フヱノキシカルボニル） ナフタレン 1. CT/JP97/03637 As a coupler component, 2-hydroxy-1,3,6-bis (benzothiazole-2'-ylaminocarbonyl) naphthalene of Example 27 (2) was used. 2-Hydroxy-1,3,6-bis (phenoxycarbonyl) Naphthalene 1. CT / JP97 / 03637
15 gに代えることの他は、 実施例 27 (2) と同様にして、 赤色粉末〔2 -ヒ ドロキシ一 1一 （2，ーメ トキシ一 5'—フヱニルァミノカルボニルフェ ニル） ァゾー 3， 6—ビス （フエノキシカルボニル） ナフタレン〕 1. 23 gを得た。 （融点 ·分解点： 328. 8°C (分解） ） 。 A red powder [2-hydroxy-11- (2, -methoxy-1-5'-phenylaminocarbonylcarbonylphenyl) azo] was prepared in the same manner as in Example 27 (2) except that the amount was changed to 15 g. 3,6-bis (phenoxycarbonyl) naphthalene] 1.23 g was obtained. (Melting point / decomposition point: 328.8 ° C (decomposition)).
実施例 77 Example 77
2—メ トキシー 1一 （2'—メ トキシ一 5'—フエニルァミノカルボニル フエニル） ァゾー^ _^ (ベンズィミダゾロン一 5' '—ィルァミノカルボ二 ル） 一 6—フヱニルァミノカルボ二ルナフタレンの合成  2-Methoxy 11- (2'-Methoxy-5'-phenylaminocarbonylphenyl) azo ^ _ ^ (benzimidazolone-1 5 ''-ylaminocarbon) 16-phenylaminocarbo Synthesis of irunaphthalene
Figure imgf000043_0001
カップラー成分として、 実施例 27 (2) の 2—ヒドロキシー 3, 6— ビス （ベンゾチアゾールー 2'—ィルァミノカルボニル） ナフタレンを、 2—メ トキシ一 3— （ベンズィミダゾロン一 5''—ィルァミノカルボニル） 一 6—フヱニルァミノカルボ二ルナフタレン 0. 95 gに代えること、 お よび撹拌時間を 100時間以上とすることの他は、 実施例 27 (2) と同 様にして、 暗いくすんだ赤色粉末〔2—メ トキシー 1— (2'—メ トキシ一 5'—フエニルァミノカルボ二ルフヱニル） ァゾー 3— (ベンズイミダゾ ロン一 5''—ィル） 一6—フエニルァミノカルボ二ルナフタ,レン〕 0. 4 1 gを得た （融点 ·分解点： 314. 3°C (分解） ） 。
Figure imgf000043_0001
As a coupler component, 2-hydroxy-3,6-bis (benzothiazole-2'-ylaminocarbonyl) naphthalene of Example 27 (2) was replaced with 2-methoxy-13- (benzimidazolone-5 ''). —Iraminocarbonyl) Same as Example 27 (2), except that 0.95 g of 1-6-phenylaminocarbonylnaphthalene is used and the stirring time is 100 hours or more. And a dark dull red powder [2-Methoxy 1- (2'-Methoxy-5'-phenylaminocarbonylcarbonyl) azo-3- (Benzimidazolone-1 5 "-yl) 16 —Phenylaminocarbonylnaphthalene, len] 0.41 g was obtained (melting point · decomposition point: 314.3 ° C. (decomposition)).
実施例 78 Example 78
2—メ トキシー 1一 （4' 一二トロフヱニルァゾ） 一 3— （ベンズィミ ダゾロン一 5" —ィルァミノカルボニル）—一 6—フヱニルァミノカルボ二 ルナフタレンの合成 2-Methoxy 11- (4'12-trophenylazo) 1-3- (Benzimi-dazolone 1-5 "-ylaminocarbonyl) -1-6-phenylaminocarbo Synthesis of Lunaphthalene
Figure imgf000044_0001
ァミン成分として実施例 7 7の 2—メ トキシ一 5—フヱニルァミノカル ボニルァニリンを、 4—二卜ロア二リン 0. 4 2 gに代えることの他は、 実施例 7 7と同様にして、 青みの赤色粉末 〔2—メ トキシー 1一 （4 ' 一 ニトロフヱニルァゾ） 一 3— (ベンズイ ミダゾロン一 5 " —ィル） 一 6— フヱニルァミノカルボ二ルナフタレン〕 1 . 1 2 gを得た。 （融点 ·分解 点 ·· 3 2 3. 3 °C (分解） ） 。
Figure imgf000044_0001
Example 77 was repeated in the same manner as in Example 77 except that 2-methoxy-5-phenylaminocarbonylylaniline of Example 77 was replaced by 0.42 g of 4-nitroaniline as a fluoramine component. Bluish red powder [2-Methoxy-11- (4'-nitrophenylazo) -13- (benzimidazolone-1 5 "-yl) -16-phenylaminocarbonylnaphthalene] 1.12 g was obtained (melting point / decomposition point: 323.3 ° C (decomposition)).
本発明ァゾ化合物はカップラーである、 2—ヒドロキシナフタレンの 3 と 6の位置に 2個のカルボキシル基 （塩を形成していてもよい） 、 カルボ キシアミ ド、 カルボキシウレイ ドまたはエステルを有していることに特徴 があり、 これから得られた色材は 2—ヒドロキシナフタレンの他の位置に それらの基を有する力ップラ一を用いた場合に比べ、 あるいは 1個のカル ボキシアミ ド、 カルボキシウレイ ドまたはエステルを有する場合に比べ、 高い耐溶剤性、 耐水性、 耐薬品性を示す。  The azo compound of the present invention has a 2-carboxyl group (which may form a salt), a carboxyamide, a carboxyureide or an ester at positions 3 and 6 of 2-hydroxynaphthalene which is a coupler. The coloring material obtained from this method is different from that obtained by using a forceps having these groups at other positions of 2-hydroxynaphthalene, or one carboxyamide, carboxyureide or Shows higher solvent resistance, water resistance and chemical resistance than those with esters.
図面の簡単な説明 BRIEF DESCRIPTION OF THE FIGURES
第 1図は実施例 1のァゾ化合物の赤外吸収スぺク トル；および第 2図は 実施例 2 3のァゾ化合物カルシウム塩の赤外吸収スぺク トルをそれぞれ示 す。  FIG. 1 shows the infrared absorption spectrum of the azo compound of Example 1; and FIG. 2 shows the infrared absorption spectrum of the azo compound calcium salt of Example 23.

Claims

情求の範囲 Range of desire
1 . 下記一般式 [ 1〕で示されるァゾ化合物 1. An azo compound represented by the following general formula [1]
Figure imgf000045_0001
Figure imgf000045_0001
〔式中、 Yは一（C O N H)n—Xまたは一 C O R、 [Wherein Y is one (CONH) n-X or one COR,
Y'は一（C〇N H)n—X'または一 C O R'、  Y ′ is one (C〇N H) n—X ′ or one COR ′,
(Xおよび X'は同じであっても異なっていてもよく、 置換基を有し ていてもよい芳香族基または置換基を有していてもよい共役二重結合を有 する複素環基）  (X and X ′ may be the same or different, and may have an aromatic group which may have a substituent or a heterocyclic group having a conjugated double bond which may have a substituent)
Rおよび R'は同じであっても異なってもよい水酸基、 炭素原子 数が 1〜6の分岐を有してもよいアルコキシ基、 ベンジルォキン基、 フエ ニルォキシ基またはフヱナシルォキシ基、 （ただし、 Rまたは R'のいすれ か一方が水酸基の場合は、 許容される塩を形成してもよい）、  R and R ′ may be the same or different and each may be a hydroxyl group, an alkoxy group having 1 to 6 carbon atoms which may have a branch, a benzyloquine group, a phenyloxy group or a phenacyloxy group, provided that R or R If either is a hydroxyl group, it may form an acceptable salt),
nは 1または 2の整数を示す、  n represents an integer of 1 or 2,
R 2は水素原子、 炭素原子数が 1〜 6の分岐を有してもよいアル キル基、 炭素原子数が 1〜 6のァシル基またはフヱニルアルキル基、 R 2 is a hydrogen atom, an alkyl group having 1 to 6 carbon atoms which may have a branch, an acyl group or a phenylalkyl group having 1 to 6 carbon atoms,
Qは炭素原子数が 1〜 6の分岐を有していてもよいアルキル基、 炭素原子数が 1〜6の分岐を有していてもよいアルコキシ基、 ハロゲン原 子、 ニトロ基またはニトロソ基、 mは 0〜3の整数 （mが 1のとき Qは 2 個の縮合環のどちらに結合していてもよく、 mが 2または 3のとき Qは一 方または両方の縮合環に結合していてもよくまた 2個の縮合環と共に環を 形成していてもよい） および Q represents an alkyl group having 1 to 6 carbon atoms which may have a branch, an alkoxy group having 1 to 6 carbon atoms which may have a branch, a halogen atom, a nitro group or a nitroso group, m is an integer of 0 to 3 (when m is 1, Q may be bonded to either of the two fused rings, and when m is 2 or 3, Q is bonded to one or both fused rings. Or a ring with two fused rings May be formed) and
Zは置換基を有していてもよい 1価の芳香族基を表す。 〕 Z represents a monovalent aromatic group which may have a substituent. ]
2. Yが—（CONH)n— Xおよび Y'が—（CONH)n— X' (n、 Xおよ び X'は前記と同意義）である請求の範囲第 1項に記載のァゾ化合物。2. The method according to claim 1, wherein Y is — (CONH) n—X and Y ′ are — (CONH) n—X ′ (n, X and X ′ are as defined above). Zo compound.
3. Zがフユニル基またはナフチル基である請求の範囲第 1項記載のァゾ 化合物。 3. The azo compound according to claim 1, wherein Z is a fuunyl group or a naphthyl group.
4. 請求の範囲第 1項に記載のァゾ化合物を含む顔料  4. Pigments containing the azo compound according to claim 1
5. 請求の範囲第 1項に記載のァゾ化合物を含む印刷ィンキ。  5. A printed ink containing the azo compound according to claim 1.
6. 請求の範囲第 1項に記載のァゾ化合物を含む塗料。  6. A paint containing the azo compound according to claim 1.
7. 請求の範囲第 1項に記載のァゾ化合物を含む高分子材料用練り込み着 色料。  7. A kneading coloring material for a polymer material containing the azo compound according to claim 1.
8. 一般式 [Π]  8. General formula [Π]
Z - NH2 [II] Z-NH 2 [II]
〔式中、 Zは置換基を有していてもよい 1価の芳香族基を表す〕で表され る芳香族アミン類をジァゾ化し、 得られたジァゾ化合物を一般式 [ΠΙ]  [Wherein, Z represents a monovalent aromatic group which may have a substituent], and the obtained diazo compound is represented by the general formula [一般]
Figure imgf000046_0001
Figure imgf000046_0001
〔式中、 Yは一（CONH)n— Xまたは一 C〇R、 [Where Y is one (CONH) n—X or one C〇R,
Υ'は一（C〇NH)n— X'または一 COR'、  Υ 'is one (C〇NH) n—X' or one COR ',
(Xおよび X'は同じであっても異なっていてもよく、 置換基を有し ていてもよい芳香族基または置換基を有していてもよい共役二重結合を有 する複素環基） 、 (X and X 'may be the same or different and each have an aromatic group which may have a substituent or a conjugated double bond which may have a substituent. Heterocyclic group),
Rおよび R'は同じであっても異なってもよい水酸基、 炭素原子 数が 1〜6の分岐を有してもよいアルコキシ基、 ベンジルォキン基、 フエ ニルォキン基またはフヱナシルォキシ基、  R and R ′ may be the same or different, a hydroxyl group, an alkoxy group having 1 to 6 carbon atoms which may have a branch, a benzyloquine group, a phenyloquine group or a phenacyloxy group,
nは 1または 2の整数、 および  n is an integer of 1 or 2, and
R 2は水素原子、 炭素原子数が 1〜 6の分岐を有してもよいアル キル基、 炭素原子数が 1〜6のァシル基またはフヱニルアルキル基、 R 2 is a hydrogen atom, an alkyl group having 1 to 6 carbon atoms which may have a branch, an acyl group or a phenylalkyl group having 1 to 6 carbon atoms,
Qは炭素原子数が 1 ~ 6の分岐を有していてもよいアルキル基、 炭素原子数が 1〜6の分岐を有していてもよいアルコキシ基、 ハロゲン原 子、 ニトロ基またはニトロソ基、 mは 0〜3の整数 （mが 1のとき Qは 2 個の縮合環のどちらに結合していてもよく、 mが 2または 3のとき Qは一 方または両方の縮合環に結合していてもよく、 また 2個の縮合環と共に環 を形成していてもよい） を示す。 〕  Q represents an alkyl group having 1 to 6 carbon atoms which may have a branch, an alkoxy group having 1 to 6 carbon atoms which may have a branch, a halogen atom, a nitro group or a nitroso group, m is an integer of 0 to 3 (when m is 1, Q may be bonded to either of two fused rings, and when m is 2 or 3, Q is bonded to one or both fused rings. And may form a ring together with the two condensed rings). ]
で表される化合物とカツプリングする（但し、 Rまたは R'が水酸基の時は 所望の金属塩を用いてレーキ化してもよい）ことを特徴とする請求の範囲 第 1項記載のァゾ化合物の製造法。 (Where R or R 'is a hydroxyl group, it may be raked using a desired metal salt). The azo compound according to claim 1, Manufacturing method.
9. Zがフニニル基またナフチル基である請求の範囲第 9項記載の製造方 法。  9. The production method according to claim 9, wherein Z is a phenyl group or a naphthyl group.
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Cited By (9)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO1998041580A1 (en) * 1997-03-19 1998-09-24 Kabushiki Kaisha Ueno Seiyaku Oyo Kenkyujo Condensed azo compound and process for producing the same
WO1999011717A1 (en) * 1997-08-28 1999-03-11 Kabushiki Kaisha Ueno Seiyaku Oyo Kenkyujo Water-soluble azo compounds and process for producing the same
WO1999033925A1 (en) * 1997-12-26 1999-07-08 Kabushiki Kaisha Ueno Seiyaku Oyo Kenkyujo Water-soluble azo compounds and process for the preparation thereof
WO2000023525A1 (en) * 1998-10-16 2000-04-27 Kabushiki Kaisha Ueno Seiyaku Oyo Kenkyujo Azo compounds and process for producing the same
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US7109376B2 (en) * 2001-02-05 2006-09-19 Dsm Ip Assets B.V. Benzene and naphthylene derivatives and their use as UV screening agents
JP2008013472A (en) * 2006-07-05 2008-01-24 Ueno Fine Chem Ind Ltd 2-naphthol derivative and mono azo compound
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Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPS51119719A (en) * 1975-03-26 1976-10-20 Rohner Ag Waterrinsoluble monoazo dye mixturs
JPS56100859A (en) * 1979-12-28 1981-08-13 Ciba Geigy Ag Monoazo pigment and method
JPS5710649A (en) * 1980-05-16 1982-01-20 Basf Ag Method of dyeing and/or printing cellulose-containing fiber material

Family Cites Families (8)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CH477536A (en) * 1966-04-23 1969-08-31 Bayer Ag Process for the production of pigment dyes
DE1644216A1 (en) * 1967-06-03 1970-12-17 Bayer Ag Azo dyes
ES358994A1 (en) * 1967-10-10 1970-11-01 Ciba Geigy Azo pigments containing a 4-carboxamido phenomorpholene-(3) group
DE2059677C3 (en) * 1970-12-04 1975-10-16 Basf Ag, 6700 Ludwigshafen Azo pigments of the beta-hydroxynaphthoic acid series, process for their production and their use
US4737581A (en) * 1984-04-25 1988-04-12 Ciba-Geigy Corporation Phenyl-azo-hydroxynaphthoic acid amide pigments containing at least one carbonamide group
DE3562683D1 (en) * 1984-08-13 1988-06-16 Agfa Gevaert Nv Process for the production of diffusion transfer images with magenta dye-releasing non-diffusable compounds
JPH0798907B2 (en) * 1989-05-17 1995-10-25 株式会社上野製薬応用研究所 Azo compound and its manufacturing method
EP0765858B1 (en) * 1995-04-12 1999-12-22 Kabushiki Kaisha Ueno Seiyaku Oyo Kenkyujo Naphthol derivatives and process for producing the same

Patent Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPS51119719A (en) * 1975-03-26 1976-10-20 Rohner Ag Waterrinsoluble monoazo dye mixturs
JPS56100859A (en) * 1979-12-28 1981-08-13 Ciba Geigy Ag Monoazo pigment and method
JPS5710649A (en) * 1980-05-16 1982-01-20 Basf Ag Method of dyeing and/or printing cellulose-containing fiber material

Cited By (14)

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WO1998041580A1 (en) * 1997-03-19 1998-09-24 Kabushiki Kaisha Ueno Seiyaku Oyo Kenkyujo Condensed azo compound and process for producing the same
US6005085A (en) * 1997-03-19 1999-12-21 Kabushiki Kaisha Ueno Seiyaku Oyo Kenkyujo Condensed azo compounds and process for preparing the same
WO1999011717A1 (en) * 1997-08-28 1999-03-11 Kabushiki Kaisha Ueno Seiyaku Oyo Kenkyujo Water-soluble azo compounds and process for producing the same
US6020470A (en) * 1997-08-28 2000-02-01 Kabushiki Kaisha Ueno Seiyaku Oyo Kenkyujo Water-soluble azo compounds and process for producing the same
WO1999033925A1 (en) * 1997-12-26 1999-07-08 Kabushiki Kaisha Ueno Seiyaku Oyo Kenkyujo Water-soluble azo compounds and process for the preparation thereof
US6409812B1 (en) 1998-10-16 2002-06-25 Kabushiki Kaisha Ueno Seiyaku Oyo Kenkyujo AZO compounds and process for producing the same
WO2000023525A1 (en) * 1998-10-16 2000-04-27 Kabushiki Kaisha Ueno Seiyaku Oyo Kenkyujo Azo compounds and process for producing the same
CN1125144C (en) * 1998-10-16 2003-10-22 株式会社上野制药应用研究所 Azo comounds and process for producing the same
US7109376B2 (en) * 2001-02-05 2006-09-19 Dsm Ip Assets B.V. Benzene and naphthylene derivatives and their use as UV screening agents
JPWO2004108833A1 (en) * 2003-06-03 2006-07-20 株式会社上野製薬応用研究所 Monoazo compound and method for producing the same
JP4515384B2 (en) * 2003-06-03 2010-07-28 上野製薬株式会社 Monoazo compound and method for producing the same
WO2005052074A1 (en) * 2003-11-28 2005-06-09 Kabushiki Kaisha Ueno Seiyaku Oyo Kenkyujo Red ink composition for color filter
JP2008013472A (en) * 2006-07-05 2008-01-24 Ueno Fine Chem Ind Ltd 2-naphthol derivative and mono azo compound
JP2013065021A (en) * 2006-11-02 2013-04-11 Dainichiseika Color & Chem Mfg Co Ltd Coating liquid for color filter pixel formation, and color filter

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JP3393869B2 (en) 2003-04-07
EP0872477A4 (en) 2002-01-02
ATE285401T1 (en) 2005-01-15
CN1105106C (en) 2003-04-09
US6084101A (en) 2000-07-04
ATE265498T1 (en) 2004-05-15
EP0872477A1 (en) 1998-10-21
DE69732022T2 (en) 2005-05-19
CN1150281C (en) 2004-05-19
KR100472978B1 (en) 2005-09-02
KR19990071483A (en) 1999-09-27
CA2240073A1 (en) 1998-04-23
EP0881267A1 (en) 1998-12-02
KR100479314B1 (en) 2006-03-23
KR19990072054A (en) 1999-09-27
DE69728860T2 (en) 2005-04-21
EP0881267A4 (en) 2003-03-05
DE69728860D1 (en) 2004-06-03
EP0881267B1 (en) 2004-04-28
DE69732022D1 (en) 2005-01-27
WO1998016513A1 (en) 1998-04-23
TW416975B (en) 2001-01-01
US5973126A (en) 1999-10-26
TW403771B (en) 2000-09-01
JP3224397B2 (en) 2001-10-29
CN1210520A (en) 1999-03-10
CN1205021A (en) 1999-01-13
EP0872477B1 (en) 2004-12-22

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